Release film, method for forming the film, and resin molding method

Abstract

To provide a release film having both excellent releasability and continuous durability even for a molded product of a curable resin composition, a film deposition method of the release film, and a resin molding method that molds a curable resin composition using a mold in which the release film is formed on a mold forming surface.SOLUTION: A release film includes a vapor-deposited film of a fluorine-based polymer and the vapor-deposited film of the fluorine-based polymer is a multilayered vapor-deposited film. A film deposition method of the release film includes performing vacuum deposition of a fluorine-based polymer on a substrate twice or more. A resin molding method includes molding a curable resin composition using a mold in which the release film is formed on a mold forming surface.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] This disclosure relates to a release film, a method for forming the same film, and a resin molding method. More specifically, it relates to a release film formed on the surface of a molded surface to release a molded product from a mold for molding a curable resin composition, a method for forming the release film on the surface of a mold, and a resin molding method using a mold coated with the release film. [Background technology]

[0002] In molding dies for optical components such as plastic lenses, metal dies (molds) made of highly rigid and dense materials such as SUS are generally used. Regardless of whether the resin is thermoplastic or curable, in resin molding, various release treatments are applied to the surface of the molded product to improve the release properties of the molded product from the above-mentioned mold.

[0003] As a method to improve the release properties of molds, surface treatments such as fluorine monolayers (Patent Document 1), fluorine vapor-deposited films (Patent Document 2), and diamond-like carbon (DLC) films (Patent Documents 3-5) are used. In addition, surface treatment methods are known to form metal films such as hard chromium plating or chromium nitride plating on the surface of mold materials to impart functions such as wear resistance, corrosion resistance, seizure resistance, lubricity, and release properties (Patent Document 6).

[0004] Furthermore, methods are known in which an external release agent such as a fluorine-based or silicone-based spray or oil component is applied to the mold and / or baked (Patent Documents 7 and 8). The above mold surface treatment and the external release agent are often used in combination.

[0005] Furthermore, in addition to the above-mentioned release treatment, release methods that utilize voltage application, ultrasonic vibrations, etc., are also known (Patent Documents 9-11). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 4444713 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 2008-24967 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2000-96233 [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2005-48252 [Patent Document 5] Japanese Unexamined Patent Application Publication No. 2007-213715 [Patent Document 6] Japanese Unexamined Patent Application Publication No. 2006-231843 [Patent Document 7] Japanese Unexamined Patent Application Publication No. 2007-63482 [Patent Document 8] Japanese Unexamined Patent Application Publication No. 2009-292089 [Patent Document 9] Japanese Unexamined Patent Application Publication No. 4-361010 [Patent Document 10] Japanese Unexamined Patent Application Publication No. 2004-74445 [Patent Document 11] Japanese Unexamined Patent Application Publication No. 2010-266664 [Patent Document 12] Japanese Unexamined Patent Application Publication No. 2008-246992 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] In molded products of curable resin compositions, such as epoxy resins, which have high adhesion and are generally difficult to release, surface treatments such as the aforementioned fluorine monolayers, fluorine vapor-deposited films, diamond-like carbon films, and metal films did not provide sufficient release properties or durability, resulting in productivity problems. Specifically, when a cationic curable resin composition was molded using a mold on which a fluorine monolayer had been formed by liquid-phase treatment, excellent release properties were not always achieved, and furthermore, the thin film thickness of a few nanometers resulted in durability problems. Fluorine vapor-deposited films had poor adhesion to the mold substrate and did not offer excellent release properties or durability. In addition, metal plating films and diamond-like carbon films had the problem of poor release properties from the initial stages of molding the curable resin composition, sometimes making release impossible. This is thought to be because a portion of the surface of the metal plating films and diamond-like carbon films is oxidized, and functional groups such as carbonyl groups are thought to be present, forming strong bonds with the polymerizable functional groups in the curable resin composition. Furthermore, diamond-like carbon films with injected fluorine components had poor adhesion to the mold substrate, resulting in the problem of the diamond-like carbon film itself peeling off.

[0008] Furthermore, in methods involving the application and baking of an external release agent, the release components are unevenly dispersed, and the application marks are transferred to the molded product, resulting in shape defects. This presents a problem in that sufficient shape accuracy cannot be obtained for optical applications. Furthermore, in demolding methods that utilize vibrations such as voltage application or ultrasonic waves, these vibrations are transmitted to the molded product, which posed problems in the molding of lenses requiring high precision, such as affecting eccentricity and thickness accuracy.

[0009] On the other hand, it is known that a release film consisting of a triazinethiol layer and a vapor-deposited layer of fluorine-based polymer exhibits excellent release properties even for molded products of curable resin compositions (Patent Document 12). However, when epoxy resin is used for continuous molding, the release properties decrease, and it could not be said that it had excellent continuous durability.

[0010] Therefore, the object of the present invention is to provide a release film that combines excellent release properties and continuous durability even for molded articles of curable resin compositions. Another object of the invention disclosed herein is to provide a novel method for forming the aforementioned release film. Furthermore, another object of the present invention is to provide a resin molding method for molding a curable resin composition using a mold on which the release film is formed on the molded surface. [Means for solving the problem]

[0011] The inventors of this disclosure conducted intensive research to solve the above-mentioned problems and found that a release film with a multilayer structure of vapor-deposited fluorine polymers maintains excellent release properties for molded articles of highly adhesive curable resin compositions such as epoxy resins, while also significantly improving continuous durability. The invention of this disclosure was completed based on these findings.

[0012] In other words, the present disclosure provides a release film comprising a vapor-deposited film of a fluorine-based polymer, wherein the vapor-deposited film of the fluorine-based polymer is a multilayer vapor-deposited film.

[0013] In the aforementioned release film, the multilayer vapor-deposited film may have a 2 to 8-layer structure.

[0014] The release film may have a thickness of 70 nm or more.

[0015] In the aforementioned release film, the fluorine-based polymer is a tetrafluoroethylene / hexafluoropropylene copolymer, 19 The number-average molecular weight determined from F-NMR may be between 10,000 and 300,000.

[0016] The release film may be formed on the mold surface of a mold for molding a curable resin composition.

[0017] In the aforementioned release film, the curable resin composition may be a curable epoxy resin composition. In the release film, the substrate constituting the mold may be at least one selected from the group consisting of stainless steel, nickel, brass, and silicon wafer.

[0018] In the aforementioned release film, a triazinethiol-treated film may be provided between the molded surface of the mold and the vapor-deposited film of the fluorine-based polymer.

[0019] Furthermore, this disclosure provides a method for forming the aforementioned release film, comprising vacuum-depositing a fluorine-based polymer onto a substrate on which the release film is to be formed two or more times.

[0020] In the above-mentioned film formation method, when depositing a fluorine-based polymer by vacuum deposition and / or after the formation of the vacuum-deposited film, a heat treatment to heat the deposited film and / or a radiation treatment to irradiate the deposited film with radiation may be performed.

[0021] In the above-mentioned film formation method, the substrate may be treated with triazinethiol before vacuum deposition.

[0022] Furthermore, this disclosure provides a resin molding method that includes molding a curable resin composition using a mold on which the release film is formed on the mold surface.

[0023] In the resin molding method described above, the curable resin composition may be a curable epoxy resin composition.

[0024] Furthermore, this disclosure provides the resin molding method for forming lenses.

[0025] In the resin molding method described above, the lens may be a wafer-level lens.

[0026] In the resin molding method described above, the lens may be a lens array. [Effects of the Invention]

[0027] Because the release film of this disclosure has the above-described structure, it maintains excellent release properties for molded products of highly adhesive curable resin compositions such as epoxy resins, while also possessing excellent continuous durability, meaning that the release properties do not deteriorate easily even after repeated molding and demolding. Therefore, in molding using curable resin compositions such as curable epoxy resin compositions, the number of continuous molding cycles before a release defect occurs can be improved, the mold change interval can be extended, and the working time due to mold removal and the productivity of molded products can be dramatically improved. In addition, the number of expensive spare molds to be kept can be reduced, and costs can be significantly improved. [Brief explanation of the drawing]

[0028] [Figure 1] Figure 1 is a schematic front view showing one embodiment of the release film deposition apparatus (vacuum deposition apparatus) of the present disclosure. [Figure 2] Figure 2 is a schematic top view showing one embodiment of the release film deposition apparatus (vacuum deposition apparatus) of the present disclosure. [Figure 3] Figure 3 is a schematic diagram (cross-sectional view) showing one embodiment of the release film of this disclosure formed on the molded surface of a mold. [Figure 4] Figure 4 is a graph showing the relationship between the number of times the fluorine-based polymer is deposited and the number of molding cycles until a release film of the present disclosure is formed on the mold. [Modes for carrying out the invention]

[0029] The release film of this disclosure includes a vapor-deposited film of a fluorine-based polymer, and the vapor-deposited film is a multilayer vapor-deposited film. Because the vapor-deposited film of the fluorine-based polymer has a multilayer structure, the thickness of the release film is increased, which improves the number of continuous molding cycles until a release defect occurs in molding using a curable resin composition, dramatically reducing the time required for mold removal and improving the productivity of molded products.

[0030] The layer structure of the multilayer vapor-deposited film of fluorine polymer is not particularly limited as long as there are two or more layers, but three or more layers are preferred, four or more layers are more preferred, and five or more layers are even more preferred. Having two or more layers of the multilayer vapor-deposited film of fluorine polymer tends to improve the continuous durability of the release film. On the other hand, there is no particular upper limit to the layer structure, but eight layers or less is preferred, seven layers or less is more preferred, and six layers or less is even more preferred. Having eight or fewer layers of the multilayer vapor-deposited film of fluorine polymer tends to reduce the surface roughness of the release film and improve the shape accuracy of the molded product.

[0031] The thickness of the release film in this disclosure is not particularly limited, but is preferably 70 nm or more, more preferably 100 nm or more, and even more preferably 130 nm or more. A thickness of 70 nm or more tends to improve the continuous durability of the release film. On the other hand, the upper limit of the thickness of the release film is not particularly limited, but is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. A thickness of 250 nm or less tends to reduce the surface roughness of the release film and improve the shape accuracy of the molded product.

[0032] The fluorine-based polymer constituting the multilayer vapor-deposited film is not particularly limited, but any polymer or copolymer of unit monomers containing an average of one or more fluorine atoms, and which is an organic polymer capable of forming a film, can be used. Examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), trifluorochloroethylene polymer (PCTFE), trifluorochloroethylene / ethylene copolymer (ECTFE), polyvinyl fluoride, fluoropolyether polymer, polyfluorosilicone, and perfluoropolymer having an aliphatic ring structure. These can be used individually or as a mixture of two or more. From the viewpoint of release properties and continuous durability of the release film, tetrafluoroethylene / hexafluoropropylene copolymer (FEP) is preferred.

[0033] The number-average molecular weight of the fluorine polymer is not particularly limited, but is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more as a lower limit, and preferably 300,000 or less, more preferably 280,000 or less, and even more preferably 250,000 or less as an upper limit. When the number-average molecular weight of the fluorine polymer is 10,000 or more, the release properties and continuous durability of the release film tend to improve. On the other hand, if the number-average molecular weight of the fluorine polymer is too high, it becomes difficult to vaporize, and vacuum deposition may not be performed smoothly. Furthermore, the number-average molecular weight of fluorine-based polymers is 19 This is determined from F-NMR.

[0034] Fluorine-based polymers preferably have functional groups within their molecules, such as unsaturated groups (double or triple bonded carbons), amino groups (-NH2), amide groups (-CONH2), carbonyl groups (-COOH), and -Si(OR)3 groups (where R is an alkyl group with 1 to 3 carbon atoms). The presence of such functional groups in fluorine-based polymers tends to improve their adhesion to metal substrates.

[0035] The substrate on which the release film of this disclosure is formed is not particularly limited, but the molded surface of a mold for molding a curable resin composition is preferred. The release film of this disclosure has high adhesion and can exhibit excellent release properties and continuous durability even with curable resin compositions that are difficult to release.

[0036] The substrate material constituting the circuit board is not particularly limited as long as it can be used in a mold by the imprint molding method, but examples include metal materials such as iron, iron alloys (stainless steel, permalloy, etc.), nickel, brass, silicon wafers, copper, copper alloys, gold, silver, cobalt, aluminum, zinc, tin, tin alloys, titanium, and chromium, with stainless steel, nickel, brass, and silicon wafers being preferred, and stainless steel and nickel being more preferred. The substrate material may be subjected to plating treatments such as electroless plating or electroforming of metal materials such as nickel, or shaping by photolithography.

[0037] The release film of this disclosure can be formed by vacuum depositing a fluorine-based polymer onto a substrate on which the release film is to be formed, two or more times. For example, a fluorine-based polymer is heated and evaporated using a vacuum deposition apparatus, and then deposited onto the metal surface of a substrate. The vacuum level is not particularly limited, but is preferably 1.0 to 1.0 × 10⁻⁶. -6 Pa, comfortable 1.0 × 10 -1 ~1.0×10 -4 The pressure is Pa. The temperature of the heater used to heat the fluorine polymer is not particularly limited, but is, for example, 200 to 400°C, preferably 270 to 360°C. However, it is not limited to this, and the optimal deposition conditions can be determined by considering the molecular weight of the fluorine polymer, the degree of vacuum, and the heater temperature.

[0038] After adjusting the vacuum level inside the apparatus to a constant level using an ionization vacuum gauge, the crucible of the evaporation source is heated with a heater to vaporize or sublimate the fluorine-based polymer. At this time, it is preferable to keep the shutter covering the substrate on which the film will be formed closed and the shutter covering the evaporation source open, confirm that the fluorine-based polymer is vaporizing or sublimating using a quartz crystal film thickness gauge or the like, adjust the evaporation rate to the desired value, and then open the shutter covering the substrate on which the film will be formed and start the deposition. By configuring it in this way, a predetermined film formation rate can be ensured.

[0039] In the vacuum deposition process described above, fluorine-based polymer molecules are heated, evaporated, sublimated, and ejected in a vacuum to deposit on the surface of the metal solid substrate. Molecules that fly from the evaporation source and deposit in a vacuum collide and react with the solid surface through processes such as the generation of crystal nuclei and diffusion, causing the thin film to grow. The formation of uniformly dispersed crystal nuclei on the solid surface influences the subsequent film growth state, resulting in film growth with regularly arranged molecules. To ensure good adhesion to the shape, it is preferable to perform deposition while changing the workpiece position and orientation.

[0040] It is preferable to perform a heat treatment to heat the deposited film and / or an irradiation treatment to irradiate the deposited film with radiation when depositing a fluorine-based polymer by vacuum deposition and / or after the formation of the vacuum-deposited film. By performing the heat treatment and / or irradiation treatment, crosslinking bonds are formed between the fluorine-based polymer and the substrate and / or between the fluorine-based polymers themselves, making it possible to create a strong release film.

[0041] The heat treatment can be performed, for example, by attaching a heater to the substrate (mold) and heating it during vacuum deposition and / or after the formation of the vacuum-deposited film. The heating temperature depends on the selection of the fluorine polymer material and the thickness of the film, but is preferably 150 to 400°C, more preferably 230 to 270°C, and even more preferably about 250°C.

[0042] For example, during vacuum deposition and / or after the formation of the vacuum-deposited film, it is desirable to irradiate the film with radiation by turning on a UV lamp placed inside the vacuum deposition apparatus. When irradiating in air after vacuum deposition film formation, a wavelength of 245-400 nm is preferred. In the case of irradiation in air, wavelengths below 280 nm are prone to oxidative degradation due to the generation of radicals by oxygen and moisture, and short wavelengths are scattered and absorbed by trace amounts of oxygen, etc. Therefore, an irradiation distance of 20 cm or less is preferred, and since the reaction rate is fast, short irradiation times are preferred and can be selected as appropriate. Also, in a vacuum (5 × 10 -3 When irradiating at approximately Pa, wavelengths of 245 nm to 400 nm are preferred. The irradiation time can be appropriately determined depending on the molecular weight of the fluorine-based polymer, temperature, etc., but irradiation for about 30 to 60 minutes is possible.

[0043] During the deposition of fluorine-based polymers, and / or after the formation of a vacuum-deposited film, heat treatment in a vacuum and / or air, and / or ultraviolet irradiation are performed. This causes the film, which has grown with molecular arrangement of fluorine-based polymers, to undergo an oxidation reaction, forming a polymerized film and creating a strong release film. Preferably, a combination of radiation irradiation and heat polymerization is desirable because it improves the durability of the resulting deposited film. For example, one method involves heating the metal substrate to be coated (230-270°C) while evaporating a fluorine-based polymer to form a film by polymerization due to heating, and irradiating it with ultraviolet light during this process. Another method involves heating the metal substrate to be coated (230-270°C) while evaporating a fluorine-based polymer to form a film, irradiating it with ultraviolet light during this process, and then, after the film formation is complete, heating (230-270°C) while irradiating it with ultraviolet light in a vacuum.

[0044] In the method for forming a release film according to this disclosure, the above-described vacuum deposition of the fluorine-based polymer is performed individually two or more times. The number of vacuum depositions is not particularly limited as long as it is two or more times, but three or more times is preferred, four or more times is more preferred, and five or more times is even more preferred. Performing vacuum deposition of the fluorine-based polymer two or more times tends to improve the continuous durability of the release film. On the other hand, there is no particular upper limit to the number of vacuum depositions, but eight times or less is preferred, seven times or less is more preferred, and six times or less is even more preferred. By limiting the number of vacuum depositions of the fluorine-based polymer to eight times or less, the surface roughness of the release film tends to be reduced, and the shape accuracy of the molded product tends to improve.

[0045] Multiple vacuum depositions of fluorinated polymers can be performed, for example, by performing heat treatment in a vacuum and / or ultraviolet irradiation as necessary during the deposition of the fluorinated polymer onto the mold in the vacuum deposition apparatus and / or after the formation of the vacuum deposition film, removing the mold from the vacuum deposition apparatus and performing heat treatment and / or ultraviolet irradiation in the atmosphere as necessary, and then returning the mold to the vacuum deposition apparatus and repeating the same operation. However, from the viewpoint of operability and manufacturing cost, it is preferable to perform vacuum deposition of the fluorinated polymer and repeated heat treatment in a vacuum as necessary within the vacuum deposition apparatus. The following describes the preferred embodiment of the film formation method for release films of this disclosure (hereinafter sometimes referred to as "film formation method of this embodiment"), but each configuration and combination thereof in each embodiment is an example, and it is possible to add, omit, substitute, and otherwise modify the configuration as appropriate without departing from the spirit of the invention of this disclosure. This disclosure is not limited by the embodiments, but is limited only by the claims.

[0046] Schematic diagrams of an example of a film deposition apparatus for the film deposition method of this embodiment are shown in Figures 1 and 2. Figure 1 is a front view, and Figure 2 is a top view. The invention will be described below with reference to the drawings, but the invention of this disclosure is not limited thereto.

[0047] The film deposition apparatus X shown in Figures 1 and 2 (hereinafter sometimes referred to as "the film deposition apparatus of this embodiment") is an embodiment of a so-called self-rotating deposition apparatus, and comprises a mold holding jig 4 for holding a mold 5, a mold holding jig rotation mechanism 3 that engages with the mold holding jig 4 and rotates the mold holding jig 4, a revolving circle plate 2 that engages with the mold holding jig rotation mechanism 3 at its outer circumference, and a mold holding jig revolution mechanism 1 that engages with the center of the revolving circle plate 2 and rotates the revolving circle plate 2, thereby causing the mold holding jig 4 to revolve, and is arranged above the inside of the vacuum deposition apparatus 100. The number of mold holding jigs 4 that are engaged with the outer circumference of the revolving circle plate 2 via the mold holding jig rotation mechanism 3 is not particularly limited, but it is preferable to engage a number selected from 2 to 8 at opposing positions. Figure 2 shows an example in which 6 mold holding jigs 4 are engaged. The mold 5 is held by the mold holding jig 4 on the back side of the mold molding surface, and is positioned so that the mold molding surface faces downward (the shape of the mold molding surface is not shown). In the film deposition apparatus of this embodiment, the mold holding jig rotation mechanism 3 has a built-in heater for heating the mold 5 (not shown). The heater built into the mold holding jig rotation mechanism 3 heats the mold 5 via the mold holding jig 4 while the fluorine-based polymer is vacuum deposited.

[0048] Furthermore, the film deposition apparatus X of this embodiment includes a crucible 6 containing a fluorine-based polymer, which is the deposition material 7, and an ultraviolet irradiation unit 9. These are located at the bottom of the inside of the vacuum deposition apparatus 100, as shown in Figure 1, and the crucible 6 and the ultraviolet irradiation unit 9 are separated to the left and right by a partition plate 11. In Figure 1, the side of the partition plate 11 where the crucible 6 is located may be referred to as the "deposition chamber," and the side of the partition plate 11 where the ultraviolet irradiation unit 9 is located may be referred to as the "ultraviolet irradiation chamber." However, the configuration is not limited to that shown in Figure 1, and the left side may be the "deposition chamber" and the right side may be the "ultraviolet irradiation chamber."

[0049] The crucible 6 is located below the deposition chamber, and the deposition material 7 is heated by a heater (not shown) and supplied with a deposition source 8 from below to the molded surface of the mold 5 located above the deposition chamber. The ultraviolet irradiation unit 9 is located below the ultraviolet irradiation chamber and irradiates the molded surface of the mold 5 located above the ultraviolet irradiation chamber with ultraviolet light 10 from below as needed.

[0050] The film deposition apparatus of this embodiment may further include components that are normally provided in a vacuum deposition apparatus, such as an intake valve 101, an exhaust valve 102, a vacuum pump 103, a film thickness gauge, and a shutter.

[0051] In the film deposition method of this embodiment, in the film deposition apparatus of this embodiment, the mold holding jig's orbital mechanism 1 rotates the orbital circle plate 2 to orbit the mold 5 held in the mold holding jig 4, while the deposition source 8 is supplied from below the deposition chamber, and ultraviolet light 10 is irradiated from below the ultraviolet irradiation chamber as needed. Alternatively, the mold holding jig's rotation mechanism 3 may be used to rotate the mold 5 while it is orbiting the mold 5. By rotating the mold 5 along with its orbit, the deposition source 8 can be uniformly deposited on the molded surface. The orbital and rotation of the mold 5 may be clockwise or counterclockwise in the top view of Figure 2. That is, the orbital and rotation may be counterclockwise as shown by the rotation arrows A and B in Figure 2, the orbital may be clockwise and the rotation counterclockwise, or the orbital may be counterclockwise and the rotation clockwise.

[0052] The rotational and orbital speeds of the mold 5 in the film deposition method of this embodiment are not particularly limited and can be appropriately set according to the supply amount of the deposition source 8 and the amount of ultraviolet irradiation.

[0053] In the film formation method of this embodiment, one layer of fluorine-based polymer vapor-deposited film is formed on the mold surface of the mold 5 during one revolution of the mold 5. Therefore, by revolving the mold 5 n times, a multilayer vapor-deposited film of n layers of fluorine-based polymer can be formed. In the film formation method of this embodiment, the thickness of the vapor-deposited fluorine polymer film (1 layer) formed during one revolution of the mold 5 can be appropriately adjusted by the revolution speed of the mold 5, etc., and is not particularly limited, but is preferably appropriately selected from the range of 30 to 70 nm, more preferably from 40 to 60 nm.

[0054] In the film formation method of this embodiment, a mold 5 can be obtained on which the release film of this disclosure is formed on the molded surface by applying heat treatment and / or radiation treatment to the vapor-deposited film formation surface of the mold 5 removed from the film formation apparatus of this embodiment, as necessary.

[0055] The release film of this disclosure may have a known release film other than a multilayer vapor-deposited film of a fluorine polymer. Examples of release films other than the vapor-deposited film of a fluorine polymer are not particularly limited, but include triazinethiol-treated films, metal films (nickel plating, chromium plating, etc.), fluorine monolayers, diamond-like carbon films, etc., each of which can be formed by methods known to the present. The release film other than the vapor-deposited film of a fluorine polymer may be formed at any of the following locations: between the substrate and the vapor-deposited film of a fluorine polymer, between the multilayer vapor-deposited film of a fluorine polymer, or on the upper surface of the multilayer vapor-deposited film of a fluorine polymer.

[0056] From the viewpoint of improving the adhesion between the multilayer vapor-deposited film of the fluorine-based polymer and the substrate metal, it is preferable to form a triazinethiol-treated film between the substrate metal and the multilayer vapor-deposited film of the fluorine-based polymer. The triazinethiol-treated film can be formed by treating the molded surface of the substrate metal with triazinethiol before vacuum deposition using the film formation method of this embodiment.

[0057] FIG. 3 is a schematic diagram (cross-sectional view) showing an embodiment of the release film of the present disclosure formed on the mold forming surface of a mold. 22 is a triazine thiol treatment film, which can be formed by subjecting the mold forming surface 23' of the mold 23 to the triazine thiol treatment described below. The release film 21 of this embodiment is a multilayer (4-layer) vapor deposition film formed by single-layer vapor deposition films 21a to 21d. The single-layer vapor deposition films 21a to 21d are formed, for example, during one revolution of the mold 23 on which the triazine thiol treatment film 22 is formed in the film formation method of the above embodiment, and a 4-layer release film 21 formed from the single-layer vapor deposition films 21a to 21d can be formed by four revolutions.

[0058] The triazine thiol treatment can form a triazine thiol treatment film on the surface of the substrate metal by a wet method using a solution containing a triazine thiol derivative represented by the following formula (1) or (2).

Chemical formula

[0059] In formula (1), R 1 is a substituent containing an unsaturated group such as alkyne (-CH≡CH-) or alkene (-C=C-). R 2 is -C m H 2m+1 (m is an integer from 1 to 18), -C n H 2n-1 (n is an integer from 1 to 18) such as -CH2CH=CH2, CH2=CH(CH2) p COOCH2CH2- (p is an integer from 1 to 10) such as COOCH2CH2-. M 1 and M 2 each represent H, or an alkali metal such as Li, Na, K, Ca.

Chemical formula

[0060] In formula (2), M 1 , M 2, and M 3 These represent either H or alkali metals such as Li, Na, K, and Ca, respectively.

[0061] Wet methods for triazinethiol treatment include immersion methods and electrolytic polymerization methods. The immersion method involves immersing metals such as copper, copper alloys, and nickel in an aqueous solution or organic solution containing a triazinethiol derivative, or a mixture thereof, for 0.1 to 120 minutes, preferably 0.5 to 30 minutes, to form a coating. In this case, the concentration of the triazinethiol derivative solution is 0.001 to 5% by weight, preferably 0.01 to 0.5% by weight, but the optimal value varies depending on the type of metal, immersion temperature, and immersion time.

[0062] Suitable organic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, toluene, ethyl cellsolve, dimethylformaldehyde, tetrahydrofuran, methyl ethyl ketone, benzene, and ethyl acetate ether.

[0063] The immersion temperature varies depending on the solution concentration and type of metal, and cannot be specified as it is determined by the solvent used. However, with water, temperatures from 1°C to 99°C are generally possible, preferably in the range of 20°C to 80°C. Immersion treatment can uniformly create a coating on metal products with complex shapes, but the resulting coating has a low degree of polymerization and is weak in strength. Therefore, after immersion, heating to 100°C or higher can be performed to transform it into a polymer coating with a high degree of polymerization. This immersion treatment method is effective for surface treatment of copper and copper alloys.

[0064] Electropolymerization is a method for forming a triazinethiol polymer film on a metal or conductor surface by electrolytic methods such as cyclic, constant current, constant potential, pulsed constant potential, and pulsed constant current, using an aqueous solution or organic solution containing a triazinethiol derivative, or a mixture thereof, with the treated metal as the anode and a platinum or stainless steel plate as the cathode. The metal is not particularly limited as long as it is conductive, and examples include iron and iron alloys (stainless steel, permalloy, etc.), copper and copper alloys, nickel, gold, silver, cobalt, aluminum, zinc, tin and tin alloys, titanium, or chromium. Conductive materials include conductive films, ITO, carbon, conductive rubber, organic conductors, etc.

[0065] The electrolytes mentioned above are not particularly limited as long as they dissolve in the solvent, exhibit electrical conductivity, and are stable. Generally, NaOH, Na2CO3, Na2SO4, K2SO3, Na2SO3, K2SO3, NaNO2, KNO2, NaNO3, NaClO4, CH3COONa, Na2B2O7, NaH2PO2, (NaPO3)6, Na2MoO4, Na3SiO3, Na2HPO3, etc., can be suitably used. From the viewpoint of the film growth rate, the concentration of these electrolytes is generally in the range of 0.001 to 1 mole, preferably 0.01 to 0.5 moles.

[0066] The solvent is preferably one that dissolves both the electrolyte and the triazinethiol derivative simultaneously, and the combination is not particularly limited. For example, water, methanol, ethanol, carbitol, cellosolve, dimethylformamide, methylpyrrolidone, acrylonitrile, ethylene carbonate, isopropyl alcohol, acetone, toluene, ethyl cellosolve, dimethylformaldehyde, tetrahydrofuran, methyl ethyl ketone, benzene, ethyl acetate ether, and the like can be used.

[0067] The concentration of the triazinethiol derivative is 0.01 to 100 mmol / L, preferably 0.1 to 10 mmol / L. The temperature of the electrolyte cannot be uniquely determined as it is related to the freezing and boiling points of the solvent, but for example, in aqueous solutions it is 1°C to 99°C, preferably 20°C to 80°C.

[0068] Any material can be used as the counter electrode (cathode) material, as long as it does not react with the electrolyte solution or has extremely low conductivity, but generally, inert conductors such as stainless steel, platinum, and carbon are used.

[0069] Furthermore, the cyclic method is performed within a potential range that does not decompose water or solvents, and this range cannot be uniquely defined as it is influenced by the type of solvent and electrolyte. The potentiometer method is -0.5 to 2V vs CES, preferably in the range from the natural potential to the oxidation potential. If the potential is lower than the natural potential, polymerization will not occur at all, and if it exceeds the oxidation potential, there is a risk of decomposition of water or solvents.

[0070] In the constant current method, the current density is 0.005 to 50 mA / cm². 2 Preferably 0.05~5mA / cm 2 This is appropriate. 0.05 mA / cm 2 If the current is lower, film growth will take too long. Also, 5 mA / cm 2 If the size is too large, cracks may form in the coating or metal leaching may occur, which is undesirable.

[0071] The electrolytic potential and electrolytic current density in the pulse method are as described above, but the time interval is 0.01 to 10 minutes, preferably 0.1 to 2 minutes. If the interval is shorter than 0.1 minutes or longer than 10 minutes, the effects of the pulse method will not be fully realized.

[0072] When pre-treating metals, any foreign substances such as organic matter must be removed. However, oxides and similar substances are not a problem as long as they do not significantly reduce the surface conductivity, and the same applies to activation treatments.

[0073] The resin molding method of this disclosure involves molding a curable resin composition using a mold on which the release film of this disclosure is formed on the mold surface. As for curable resin compositions, from the viewpoint of mass productionability and moldability of resin molded products, resins that cure in a short time and have excellent heat resistance are preferred. Examples include epoxy-based cationic curable resin compositions, acrylic-based radical curable resin compositions, and curable silicone resin compositions. Among these, epoxy-based cationic curable resin compositions (curable epoxy resin compositions) that cure in a short time, have a short casting time to the mold, have a small curing shrinkage rate and excellent dimensional stability, and are not affected by oxygen inhibition during curing are preferred.

[0074] As the epoxy resin, known or conventional compounds having one or more epoxy groups (oxirane rings) in the molecule can be used, such as alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds. In this disclosure, among these, polyfunctional alicyclic epoxy compounds having an alicyclic structure and two or more epoxy groups as functional groups in one molecule are preferred because they can form cured products with excellent heat resistance and transparency.

[0075] The aforementioned polyfunctional alicyclic epoxy compound is, specifically, (i) Compounds having an epoxy group (i.e., an alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom that constitute an alicyclic ring. (ii) Compounds having an epoxy group directly attached to the alicyclic ring by a single bond. (iii) Compounds having an alicyclic ring and a glycidyl group These are some examples.

[0076] Examples of the compound (i) having an alicyclic epoxy group as described above include the compound represented by the following formula (i). [ka]

[0077] In formula (i) above, X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of such linking groups include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and groups formed by linking multiple such groups. Note that the cyclohexene oxide group in formula (i) may have substituents (e.g., alkyl groups) attached to it.

[0078] Examples of the above-mentioned divalent hydrocarbon groups include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene groups, methylmethylene groups, dimethylmethylene groups, ethylene groups, propylene groups, and trimethylene groups. Examples of the above-mentioned divalent alicyclic hydrocarbon groups include cycloalkylene groups (including cycloalkylidene groups) such as 1,2-cyclopentylene groups, 1,3-cyclopentylene groups, cyclopentylidene groups, 1,2-cyclohexylene groups, 1,3-cyclohexylene groups, 1,4-cyclohexylene groups, and cyclohexylidene groups.

[0079] Examples of alkenylene groups in which part or all of the carbon-carbon double bonds are epoxidized (sometimes referred to as "epoxidized alkenylene groups") include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene groups, propenylene groups, 1-butenylene groups, 2-butenylene groups, butadienylene groups, pentenylene groups, hexenylene groups, heptenylene groups, and octenylene groups. Preferably, the epoxidized alkenylene group is an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, and more preferably, an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized.

[0080] The linking group in X above is preferably a linking group containing an oxygen atom, specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-, epoxidized alkenylene group; a group in which multiple of these groups are linked; a group in which one or more of these groups are linked to one or more of the divalent hydrocarbon groups.

[0081] Typical examples of compounds represented by formula (i) above include (3,4,3',4'-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, and compounds represented by the following formulas (i-1) to (i-10). In formula (i-5) below, L is an alkylene group having 1 to 8 carbon atoms, and among these, linear or branched alkylene groups having 1 to 3 carbon atoms, such as methylene, ethylene, propylene, and isopropylene groups, are preferred. In formulas (i-5), (i-7), (i-9), and (i-10) below, n 1 ~n 8 Each of these represents an integer between 1 and 30.

[0082] [ka] [ka]

[0083] The compound (i) having an alicyclic epoxy group as described above also includes epoxy-modified siloxanes.

[0084] Examples of epoxy-modified siloxanes include linear or cyclic polyorganosiloxanes having a structural unit represented by the following formula (i'). [ka]

[0085] In the above equation (i'), R 1 R represents a substituent containing an epoxy group represented by the following formula (1a) or (1b), 2 This indicates an alkyl group or alkoxy group.

[0086] [ka]

[0087] In the formula, R 1a , R 1b These represent identical or different linear or branched alkylene groups, such as linear or branched alkylene groups having 1 to 10 carbon atoms, including methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and decamethylene group.

[0088] The epoxy equivalent of the epoxy-modified siloxane (according to JIS K7236) is, for example, 100 to 400, preferably 150 to 300.

[0089] As the epoxy-modified siloxane, commercially available products such as the epoxy-modified cyclic polyorganosiloxane represented by the following formula (i'-1) (trade name "X-40-2670", manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. [ka]

[0090] Examples of compounds (ii) having an epoxy group directly bonded by a single bond to the alicyclic ring mentioned above include the compound represented by the following formula (ii). [ka]

[0091] In formula (ii), R' is a group obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol (a p-valent organic group), and is p, n 9Each represents a natural number. p-valence alcohol [R'-(OH) p Examples of polyhydric alcohols (alcohols with 1 to 15 carbon atoms, etc.) such as 2,2-bis(hydroxymethyl)-1-butanol. p is preferably 1 to 6, and n 9 1 to 30 is preferred. If p is 2 or greater, n in the base within each square bracket (outer bracket) 9 These may be the same or different. Specific examples of compounds represented by formula (ii) above include the 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [for example, trade name "EHPE3150" (manufactured by Daicel Corporation)].

[0092] Examples of the compounds (iii) having the alicyclic ring and glycidyl group mentioned above include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated biphenol-type epoxy compounds, hydrogenated phenol novolac-type epoxy compounds, hydrogenated cresol novolac-type epoxy compounds, hydrogenated cresol novolac-type epoxy compounds of bisphenol A, hydrogenated naphthalene-type epoxy compounds, hydrogenated trisphenolmethane-type epoxy compounds, and other hydrogenated aromatic glycidyl ether epoxy compounds.

[0093] As for the polyfunctional alicyclic epoxy compound, compound (i) having an alicyclic epoxy group is preferred because it yields a cured product with high surface hardness and excellent transparency, and the compound represented by the above formula (i) (for example, (3,4,3',4'-diepoxy)bicyclohexyl) is more preferred.

[0094] The curable resin composition in this disclosure may contain other curable compounds in addition to epoxy resins as curable compounds, for example, one or more cationic curable compounds such as oxetane compounds and vinyl ether compounds.

[0095] The proportion of epoxy resin in the total amount (100% by weight) of curable compounds contained in the curable resin composition is, for example, 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and even more preferably 80% by weight or more. The upper limit is, for example, 100% by weight, preferably 90% by weight.

[0096] Furthermore, the proportion of compound (i) having an alicyclic epoxy group in the total amount (100% by weight) of curable compounds contained in the curable resin composition is, for example, 20% by weight or more, preferably 30% by weight or more, and more preferably 40% by weight or more. The upper limit is, for example, 70% by weight, preferably 60% by weight.

[0097] Furthermore, the proportion of the compound represented by formula (i) in the total amount (100% by weight) of curable compounds contained in the curable resin composition is, for example, 10% by weight or more, preferably 15% by weight or more, and more preferably 20% by weight or more. The upper limit is, for example, 50% by weight, preferably 40% by weight.

[0098] The curable resin composition preferably contains a polymerization initiator together with the curable compound, and more preferably contains one or more photo- or thermal polymerization initiators (for example, photo- or thermal cationic polymerization initiators).

[0099] A photocationic polymerization initiator is a compound that generates acid upon irradiation with light, thereby initiating the curing reaction of a curable compound (e.g., a cationic curable compound) contained in a curable composition. It consists of a cation part that absorbs light and an anion part that is the source of acid generation.

[0100] Examples of photocationic polymerization initiators include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, and bromine salt compounds.

[0101] In this disclosure, the use of sulfonium salt compounds is particularly preferred because it allows for the formation of cured products with excellent curability. Examples of cations in sulfonium salt compounds include aryl sulfonium ions such as (4-hydroxyphenyl)methylbenzylsulfonium ions, triphenylsulfonium ions, diphenyl[4-(phenylthio)phenyl]sulfonium ions, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium ions, and tri-p-tolylsulfonium ions (e.g., triarylsulfonium ions).

[0102] For example, the anionic portion of the photocationic polymerization initiator is [(Y) s B(Phf) 4-s ] - (In the formula, Y represents a phenyl group or a biphenylyl group. Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from perfluoroalkyl groups, perfluoroalkoxy groups, and halogen atoms. s is an integer from 0 to 3), BF4 - [(Rf) t PF 6-t ] - (In the formula, Rf represents an alkyl group in which 80% or more of the hydrogen atoms are replaced by fluorine atoms. t represents an integer from 0 to 5.) AsF6 - SbF6 - , SbF5OH - These are some examples.

[0103] Examples of photocationic polymerization initiators include (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium Tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide, phenyltris(pentafluorophenyl)borate, [4-(2-thiooxantonylthio)phenyl]phenyl-2-thiooxantonylsulfonium, phenyltris(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonium Hexafluoroantimonate, product names "Cyracure UVI-6970", "Cyracure UVI-6974", "Cyracure UVI-6990", "Cyracure UVI-950" (all manufactured by Union Carbide, USA), "Irgacure 250", "Irgacure 261", "Irgacure 264", "CG-24-61" (all manufactured by BASF), "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" (all manufactured by ADEKA Corporation), "DAICAT"II" (manufactured by Daicel Corporation), "UVAC1590", "UVAC1591" (both manufactured by Daicel Cytec Corporation), "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (all manufactured by Nippon Soda Co., Ltd.), "PI-2074" (manufactured by Rhodia Corporation, tetrakis(pentafluorophenyl) borate) Commercially available products such as toricumyliodonium salt, "FFC509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (all manufactured by Midori Chemical Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartomer, USA), "CPI-100P", "CPI-101A" (both manufactured by Sunapro Co., Ltd.) can be used.

[0104] A thermal cationic polymerization initiator is a compound that generates acid when subjected to heat treatment, thereby initiating the curing reaction of a cationic curable compound contained in a curable composition. It consists of a cation part that absorbs heat and an anion part that is the source of acid generation. A thermal cationic polymerization initiator can be used alone or in combination of two or more types.

[0105] Examples of thermal cationic polymerization initiators include iodonium salt compounds and sulfonium salt compounds.

[0106] Examples of cationic moieties for thermal cationic polymerization initiators include 4-hydroxyphenyl-methyl-benzylsulfonium ions, 4-hydroxyphenyl-methyl-(2-methylbenzyl)sulfonium ions, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium ions, and p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium ions.

[0107] Examples of the anionic portion of the thermal cationic polymerization initiator can be the same as those of the anionic portion of the photocatalytic cationic polymerization initiator described above.

[0108] Examples of thermal cationic polymerization initiators include 4-hydroxyphenyl-methyl-benzylsulfonium phenyltris(pentafluorophenyl)borate, 4-hydroxyphenyl-methyl-(2-methylbenzyl)sulfonium phenyltris(pentafluorophenyl)borate, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium phenyltris(pentafluorophenyl)borate, and p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium phenyltris(pentafluorophenyl)borate.

[0109] The polymerization initiator content is, for example, in the range of 0.1 to 5.0 parts by weight per 100 parts by weight of the curable compound (e.g., a cationic curable compound) contained in the thermosetting resin composition. If the polymerization initiator content falls below the above range, curing failure may occur. On the other hand, if the polymerization initiator content exceeds the above range, the cured product tends to become more discolored.

[0110] The thermosetting resin composition in this disclosure can be produced by mixing the above-mentioned curable compound with a polymerization initiator and, if necessary, other components (e.g., solvents, antioxidants, surface modifiers, photosensitizers, defoamers, leveling agents, coupling agents, surfactants, flame retardants, ultraviolet absorbers, colorants, etc.). The amount of other components is, for example, 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, of the total amount of the curable composition.

[0111] As the thermosetting resin composition in this disclosure, commercially available products such as "CELVENUS OUH106" and "CELVENUS OTM107" (both manufactured by Daicel Corporation) can be used.

[0112] Examples of methods for molding a curable resin composition using a mold on which the release film of this disclosure is formed on the mold surface include the following methods (1) and (2). (1) A method in which a curable resin composition is applied to a mold, a substrate is pressed onto it, the curable resin composition is cured, and then the mold is removed. (2) A method in which a curable resin composition is applied to at least one of the upper and lower molds (preferably the lower mold), the upper and lower molds are joined together and the curable resin composition is cured, and then the upper and lower molds are separated.

[0113] For example, when using a photocurable resin composition as the curable resin composition, it is preferable to use a substrate having a light transmittance of 90% or more at a wavelength of 400 nm, and substrates made of quartz or glass can be suitably used. The light transmittance at the aforementioned wavelength can be determined by using a substrate (thickness: 1 mm) as a test piece and measuring the light transmittance at the aforementioned wavelength irradiated onto the test piece using a spectrophotometer.

[0114] There are no particular restrictions on the method of applying the curable resin composition; for example, methods using a dispenser or syringe can be used. Furthermore, it is preferable to apply the curable resin composition to the center of the mold.

[0115] Curing of a curable resin composition can be performed, for example, by irradiation with ultraviolet light when using a photocurable resin composition. Light sources used for ultraviolet irradiation include high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, and metal halide lamps. The irradiation time varies depending on the type of light source, the distance between the light source and the coated surface, and other conditions, but is no longer than several tens of seconds. The illuminance is approximately 5 to 200 mW. After ultraviolet irradiation, heating (post-curing) may be performed as needed to accelerate curing.

[0116] For example, when using a thermosetting resin composition as the curable resin composition, the curable composition can be cured by heat treatment. The heating temperature is, for example, around 60 to 150°C. Setting the molding heating temperature lower than the deposition temperature of the fluorine-based polymer tends to suppress the deterioration of the performance of the deposited film. The heating time is, for example, around 0.5 to 20 hours.

[0117] The molded product obtained by the resin molding method of this disclosure can be easily released from the mold because the molded surface of the mold is covered with the release film of this disclosure. Furthermore, since the release film of this disclosure has extremely high continuous durability, the number of molding cycles before release failure occurs can be increased, extending the mold change interval and dramatically improving the time required for mold removal and the productivity of molded products. In addition, the number of expensive spare molds to be kept can be reduced, resulting in a significant improvement in costs.

[0118] The molded articles obtained by the resin molding method of this disclosure are not particularly limited, but are molded in a mold coated with the release film of this disclosure. Because the molding accuracy is extremely high, it is preferably adapted for optical components, such as lenses, prisms, optical panels, microlenses, head-up displays, mirrors, windows, and optical filters, and can be suitably used for lenses that require high molding accuracy.

[0119] The type and shape of the lens are not particularly limited, but examples include eyeglass lenses, optical instrument lenses, optoelectronic lenses, laser lenses, pickup lenses, automotive camera lenses, mobile phone camera lenses, digital camera lenses, OHP lenses, Fresnel lenses, microlenses, wafer-level lenses, etc., and it is preferably applied to wafer-level lenses that require small size, thinness, and high precision.

[0120] When forming lenses by the resin molding method of this disclosure, a lens array is preferred from the viewpoint of production efficiency. A lens array has a configuration in which two or more lenses are arranged two-dimensionally and these lenses are connected to each other via joints. In the case of a wafer-level lens array, the diameter of the lenses is, for example, 1 to 5 mm. The width of the joint is, for example, 1 mm or less, preferably 0.05 to 1 mm, and more preferably 0.05 to 0.5 mm.

[0121] There are no particular limitations on the means for separating the lens array into individual components, and well-known and conventional methods can be employed, but it is preferable to use a high-speed rotating blade.

[0122] When cutting using a high-speed rotating blade, the blade's rotation speed is typically around 10,000 to 50,000 revolutions per minute. Furthermore, since frictional heat is generated when cutting a lens array using a high-speed rotating blade, it is preferable to cool the lens array during cutting to prevent deformation of the lenses and deterioration of their optical properties due to frictional heat.

[0123] A lens obtained by cutting a lens array at the lens joint includes the lens portion and its peripheral portion. Lenses obtained in this way can be suitably used as sensor lenses and camera lenses for mobile electronic devices such as mobile phones and smartphones.

[0124] Each aspect disclosed herein can be combined with any other features disclosed herein. [Examples]

[0125] The present invention will be described in more detail below based on examples, but each configuration and combination thereof in each embodiment is merely an example, and additions, omissions, substitutions, and other modifications can be made as appropriate without departing from the spirit of the present invention. This disclosure is not limited by the embodiments, but is limited only by the claims.

[0126] Manufacturing Example 1: Formation of a triazinethiol-treated layer Using a stainless steel mold (diameter: 10 cm) with lens cavities (diameter: 3 mm, depth: 0.5 mm) arranged in a two-dimensional pattern (10 rows vertically x 10 rows horizontally), an aqueous solution of 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium salt (DAN) (1.3 g / L) and sodium nitrite (7 g / L) was placed in an electrolytic cell and electrolytically treated at 1.5 V at 40°C for 5 minutes to form a triazinethiol-treated layer on the molded surface. In the electrolyte cell, the mold was used as the anode and the counter electrode as the cathode.

[0127] Example 1 (Use as an example) Vacuum deposition of fluorine-based polymers In the mold holding jig 4 of the orbital vacuum deposition apparatus 100 shown in Figure 1, the back surface of the mold obtained in Manufacturing Example 1 was fixed so that the mold surface faced downwards, and the deposition material 7 (tetrafluoroethylene / hexafluoropropylene copolymer (FEP)) was added to the crucible 6. The vacuum pump 103 was operated, and the vacuum level measured by an ionization vacuum gauge (not shown) was 5 × 10⁻⁶. -4 Once Pa was reached, the crucible 6 was heated to raise the temperature of the deposition material 7 to 275°C, and the revolution and rotation of the mold were started. During the revolution, the ultraviolet irradiation unit 9 remained off, and the mold was heated by a heater built into the mold holding jig rotation mechanism 3. After two revolutions, a mold was obtained in which the molded surface was coated with a release film consisting of two layers of deposited fluorine polymer. The film thickness measured by a quartz crystal film thickness gauge (not shown) installed in the vacuum deposition apparatus 100 was 74.5 nm. The surface roughness of the release film measured by a laser microscope (product name "LEXT OLS4100", manufactured by Olympus Corporation) was Sa (Ra) 8 nm and Sz (Rz) 131 nm.

[0128] Examples 2-7 (Example 2 is for reference only) The procedure was the same as in Example 1, except that the mold was revolved 3 to 8 times. In each case, a mold was obtained in which the molded surface was coated with a release film consisting of 3 to 8 layers of vapor-deposited fluorine polymer. The film thickness and surface roughness are shown in Table 1.

[0129] Comparative Example 1 The procedure was the same as in Example 1, except that the mold was revolved only once, and a mold was obtained coated with a release film in which a single layer of fluorine-based polymer vapor-deposited film was formed on the molded surface. The film thickness and surface roughness are shown in Table 1.

[0130] [Table 1]

[0131] Experimental Example 1: Evaluation of the number of molding cycles required before mold release failure occurs. In the center of the molds obtained in Examples 1-7 and Comparative Example 1, a curable resin composition (product name "CELVENUS OTM107", manufactured by Daicel Corporation) was applied using a volumetric dispensing dispenser (Step I). Subsequently, the coated curable resin composition was subjected to heat treatment (80°C for 1 minute - 170°C for 2 minutes - 100°C for 1 minute) (Step II), followed by demolding (Step III), to obtain a circular lens array having a configuration in which 100 lenses are arranged in 10 vertical x 10 horizontal rows, and these lenses are connected to each other via joints. Subsequently, the mold was used again for the above steps I to III, and this was repeated until the lens array failed to release (specifically, until the negative pressure detected by the load cell reached -50N) to evaluate continuous durability. Figure 4 shows a graph illustrating the relationship between the number of times the fluorine polymer was deposited (corresponding to the number of fluorine polymer deposition layers) and the number of molding cycles until release failure occurred. [Industrial applicability]

[0132] The release film of the present invention maintains excellent release properties for molded articles of highly adhesive curable resin compositions such as epoxy resins, while also possessing excellent continuous durability, meaning that the release properties do not deteriorate even after repeated molding and demolding. Therefore, it can be suitably used as a release film for molds used in molding curable resin compositions such as curable epoxy resin compositions. [Explanation of Symbols]

[0133] X Thin film deposition equipment (vacuum deposition equipment) 1. Mold holding jig revolution mechanism 2. Orbital Circle Board 3. Rotation mechanism of mold holding jig 4. Mold holding jig 5. Mold 6 Crucible 7 Deposition material 8 Vapor deposition source 9 Ultraviolet irradiation machine 10 Ultraviolet rays 11 partition plates 100 Vacuum deposition apparatus 101 Intake valve 102 Exhaust valve 103 Vacuum pump 21 Release film (multilayer vapor deposition film) 21a~21d Single-layer vapor-deposited film 22 Triazinethiol-treated film 23 molds 23' Molded surface

Claims

1. A method for producing a molded article, comprising: using a mold that includes a vapor-deposited film of a fluorine-based polymer, wherein the vapor-deposited film of the fluorine-based polymer is a multilayer vapor-deposited film, and a release film having a thickness of 130 nm or more and 250 nm or less is formed on the molded surface, a curable resin composition is molded to obtain a molded article.

2. The method for manufacturing a molded article according to claim 1, wherein the multilayer vapor-deposited film has a 4 to 8-layer structure.

3. The fluorine-based polymer is a tetrafluoroethylene / hexafluoropropylene copolymer, 19 A method for producing a molded article according to claim 1 or 2, wherein the number average molecular weight determined from F-NMR is 10,000 to 300,000.

4. A method for manufacturing a molded article according to any one of claims 1 to 3, wherein the curable resin composition is a curable epoxy resin composition.

5. A method for manufacturing a molded article according to any one of claims 1 to 4, wherein the base material constituting the mold is at least one selected from the group consisting of stainless steel, nickel, brass, and silicon wafer.

6. A method for manufacturing a molded article according to any one of claims 1 to 5, wherein a triazinethiol-treated film is provided between the molded surface of the mold and the vapor-deposited film of a fluorine-based polymer.

7. The method for manufacturing a molded article according to any one of claims 1 to 6, wherein the molded article is a lens.

8. The method for manufacturing a molded article according to claim 7, wherein the lens is a wafer-level lens.

9. The method for manufacturing a molded article according to claim 7 or 8, wherein the lens is a lens array.

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