WO2024019039A1 - Film stratifié et procédé de production de film stratifié - Google Patents

Film stratifié et procédé de production de film stratifié Download PDF

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Publication number
WO2024019039A1
WO2024019039A1 PCT/JP2023/026229 JP2023026229W WO2024019039A1 WO 2024019039 A1 WO2024019039 A1 WO 2024019039A1 JP 2023026229 W JP2023026229 W JP 2023026229W WO 2024019039 A1 WO2024019039 A1 WO 2024019039A1
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Prior art keywords
resin sheet
release layer
less
resin
film
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PCT/JP2023/026229
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English (en)
Japanese (ja)
Inventor
由佳 天野
充晴 中谷
侑司 小野
武士 久保
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東洋紡株式会社
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Publication of WO2024019039A1 publication Critical patent/WO2024019039A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating

Definitions

  • the present invention relates to a laminated film in which resin sheets are laminated.
  • the present invention relates to a laminated film in which resin sheets are laminated for use in electronic components and optical applications.
  • release films based on polyester films have high heat resistance and mechanical properties, and are used as process films for solution casting of resin sheets such as adhesive sheets, cover films, polymer electrolyte membranes, and dielectric resin sheets. has been used as.
  • resin sheets used for electronic components and optical applications such as dielectric resin sheets used in film capacitors, are required to have high smoothness and transparency. High smoothness has also been required. For this reason, techniques such as those described in Patent Documents 1 to 3 have been disclosed, and a mold release layer having a lower surface roughness has been proposed.
  • Patent Document 4 proposes adding specific particles into a resin sheet used for optical purposes such as a polarizing plate to impart slipperiness.
  • Patent Document 5 proposes a method of transferring particles on a base film to a resin sheet used for a film for a film capacitor or the like.
  • the present invention solves the above problems and proposes a laminated film that can provide a resin sheet that is highly smooth and has good sliding properties without substantially adding particles inside the resin sheet.
  • a laminate having a release layer disposed on at least one side of a smooth base film, and a resin sheet disposed on the opposite side of the release layer from the base material includes a resin sheet obtained by curing a resin sheet forming composition containing at least the resin according to the present invention and a crosslinking agent. Further, the resin sheet can have irregularities due to the phase separation structure on the film surface by coating, drying and curing under the conditions described in this specification. Furthermore, the present inventors have discovered that good slipperiness is developed when at least a part of the components forming the mold release layer transfers to the resin sheet on the surface of the resin sheet on the mold release layer side. Ta.
  • the resin sheet of the present invention has the surface free energy of the surface (2) on the release layer side of the resin sheet measured after peeling the resin sheet from the laminated film by appropriately transferring the release component from the release layer. can be reduced to 45 mJ/ m2 or less. Further, although it should not be limited to a specific theory, the resin sheet according to the present invention has surface irregularities and lowers the surface free energy of the surface (2) on the mold release layer side of the resin sheet. Without impairing the physical properties required for the sheet, the resin sheet has been successfully made to have good sliding properties without substantially containing particles.
  • the present invention has the following configuration.
  • Laminated film that satisfies the following:
  • the resin sheet is obtained by curing a resin sheet forming composition containing at least a resin component (A) and a crosslinking agent (B),
  • the resin sheet contains substantially no particles
  • the film thickness (t1) of the resin sheet is 1 ⁇ m or more and 20 ⁇ m or less
  • the arithmetic mean height (Sa) of the surface (1) of the resin sheet opposite to the release layer is 2 nm or more and 30 nm or less
  • the surface free energy of the surface (2) of the resin sheet on the release layer side, measured after peeling the resin sheet from the laminated film, is 45 mJ/m 2 or less
  • the present invention provides a method for producing a laminated film according to any one of [1] to [7] above, which comprises applying a resin sheet onto the release layer by a solution casting method.
  • a method of manufacturing a laminated film is provided.
  • the laminated film of the present invention it is possible to provide a resin sheet that is highly smooth and has good sliding properties, and by using the resin sheet molded according to the present invention, it is possible to provide products that are good for various uses. be able to.
  • FIG. 1 is a schematic cross-sectional view showing the configuration of the present invention.
  • FIG. 1 is a schematic cross-sectional view illustrating the configuration of the present invention in one embodiment.
  • the resin sheet can have high smoothness and slipperiness in a well-balanced manner, and can suppress a decrease in yield that may occur during the conveyance process, for example.
  • the present invention can provide a good balance of high smoothness and slipperiness, thereby improving electrical properties such as dielectric breakdown voltage. Can be done.
  • the present invention can suppress winding misalignment and wrinkles when winding a dielectric resin sheet or the like onto a roll, thereby making it possible to obtain a good roll. Therefore, for example, it becomes easier to control the performance of a film capacitor as designed.
  • the resin sheet does not substantially contain particles, it is possible to prevent particles from slipping off during the manufacturing process, and it is possible to obtain resin sheets with higher precision, such as dielectric resin sheets and film capacitors. .
  • the present invention includes a polyester base film, a release layer disposed on at least one side of the base film, and a resin sheet disposed on the surface of the release layer opposite to the base material. death, Laminated film that meets the following conditions:
  • the resin sheet is obtained by curing a resin sheet forming composition containing at least a resin component (A) and a crosslinking agent (B),
  • the resin sheet contains substantially no particles
  • the film thickness (t1) of the resin sheet is 1 ⁇ m or more and 20 ⁇ m or less
  • the arithmetic mean height (Sa) of the surface (1) of the resin sheet opposite to the release layer is 2 nm or more and 30 nm or less
  • the surface free energy of the surface (2) of the resin sheet on the release layer side, measured after peeling the resin sheet from the laminated film, is 45 mJ/m 2 or less
  • the laminated film of the present invention includes a polyester base film 10, a release layer 11 disposed on at least one side of the base film 10, and a base film 10 in the release layer 11. is a laminated film having a resin sheet 12 disposed on the opposite surface.
  • This invention can provide the resin sheet which can improve transparency etc. for an optical use, for example, Comprising: Moreover, it can provide the resin sheet which shows high smoothness. Moreover, it was previously difficult to It is possible to achieve both high smoothness and high slipperiness, and for example, it is possible to suppress scratches during the transportation process, and to avoid a decrease in yield. Furthermore, for electronic component applications such as film capacitor applications, a resin sheet that exhibits high smoothness can be provided, and the resin sheet can improve electrical properties such as dielectric breakdown voltage.
  • the resin sheet does not substantially contain particles, and it is possible to avoid insufficient transparency such as increased internal haze. Further, it is possible to avoid the problem of non-uniformity in the amount of particles transferred to the resin sheet, and it is possible to exhibit good slipperiness.
  • the present invention has a polyester base film.
  • the polyester constituting the polyester film used as the base material of the present invention is not particularly limited, and a polyester film formed from a polyester commonly used as a base film can be used.
  • it is a crystalline linear saturated polyester consisting of an aromatic dibasic acid component and a diol component, such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, or these. More preferred is a copolymer whose main component is a constituent component of the resin.
  • polyester films formed from polyethylene terephthalate are particularly suitable.
  • the repeating units of ethylene terephthalate are preferably 90 mol% or more, more preferably 95 mol% or more, and a small amount of other dicarboxylic acid components and diol components may be copolymerized. From the viewpoint of cost, it is preferred to use only terephthalic acid and ethylene glycol. Further, known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallizing agents, etc. may be added within a range that does not impede the effects of the film of the present invention.
  • the polyester film is preferably a biaxially oriented polyester film for reasons such as high elastic modulus in both directions.
  • the intrinsic viscosity of the polyethylene terephthalate film is preferably 0.50 to 0.70 dl/g, more preferably 0.52 to 0.62 dl/g.
  • the intrinsic viscosity is 0.50 dl/g or more, it is preferable because many breaks do not occur during the stretching process.
  • it is 0.70 dl/g or less it is preferable because the cutting properties are good when cutting into a predetermined product width and dimensional defects do not occur. Further, it is preferable that the raw material pellets be sufficiently vacuum dried.
  • the method for producing the polyester film in the present invention is not particularly limited, and conventionally commonly used methods can be used.
  • it can be obtained by melting the polyester in an extruder, extruding it into a film, cooling it in a rotating cooling drum to obtain an unstretched film, and then stretching the unstretched film.
  • the stretching is preferably biaxial stretching from the viewpoint of mechanical properties.
  • a biaxially stretched film can be obtained by sequentially biaxially stretching a uniaxially stretched film in the longitudinal or transverse direction in the transverse or longitudinal direction, or by simultaneously biaxially stretching an unstretched film in the longitudinal and transverse directions. I can do it.
  • the stretching temperature during stretching of the polyester film is preferably at least the secondary transition point (Tg) of the polyester. It is preferable to stretch the film 1 to 8 times, particularly 2 to 6 times, in both the longitudinal and transverse directions.
  • the thickness of the polyester film is preferably 6 ⁇ m or more and 50 ⁇ m or less, more preferably 8 ⁇ m or more and 31 ⁇ m or less, and even more preferably 10 ⁇ m or more and 28 ⁇ m or less. If the thickness of the film is 6 ⁇ m or more, it is preferable because there is no risk of deformation due to heat during film production, processing of a release layer, molding of a resin sheet, and the like. On the other hand, if the thickness of the film is 50 ⁇ m or less, the diameter when wound into a roll is small and the length of the resin sheet to be formed can be increased, which is preferable. When the polyester film as the base film has the multilayer structure described below, the thickness of the base film as a whole falls within the above range.
  • the polyester film may be a single layer or a multilayer of two or more layers. It is preferable that at least one side has a surface layer A that is substantially free of particles. In one embodiment, the polyester film that is the base film has a surface layer A on the resin sheet side. When the base film is a laminated polyester film having a multilayer structure of two or more layers, a surface layer B that can contain particles etc. may be provided on the opposite side of the surface layer A that does not substantially contain particles. preferable.
  • the layer structure in the thickness direction is A/B, or Examples include laminated structures such as A/C/B.
  • Layer C may have a plurality of layers.
  • the surface layer B may not contain particles. In that case, it is preferable to provide a coating layer containing particles and a binder on the surface layer B in order to provide slipperiness for winding the film into a roll.
  • the surface layer A located on the surface on which the resin sheet is formed does not substantially contain particles.
  • the arithmetic mean height (Sa) of the surface layer A of the polyester film that is, the arithmetic mean height (Sa) of the release layer side surface of the base film is preferably 20 nm or less. Furthermore, it is particularly preferable that the arithmetic mean height (Sa) is 10 nm or less. When Sa is 20 nm or less, pinholes and local thickness unevenness are less likely to occur during molding of the resin sheet, which is preferable.
  • the release layer does not substantially contain particles, and the arithmetic mean height (Sa) after lamination of the release layer is within the above range. It is preferable to enter.
  • substantially free of particles means, for example, in the case of inorganic particles, the amount of inorganic elements determined by fluorescent X-ray analysis is 50 ppm or less, preferably 10 ppm or less, and most preferably below the detection limit. This means the content.
  • the maximum protrusion height (P) of the surface layer A of the polyester film that is, the maximum protrusion height (P) of the release layer side surface of the base film is, for example, 500 nm or less, preferably 200 nm or less, The thickness is more preferably 150 nm or less, even more preferably 100 nm or less, for example 85 nm or less, particularly preferably 50 nm or less. If the maximum protrusion height (P) is 500 nm or less, defects such as pinholes and local thinning will not occur during the formation of the resin sheet, and the yield will be good, which is preferable.
  • P in the surface layer A of the polyester film is preferably as small as possible, but it may be 1 nm or more, or 3 nm or more.
  • P maximum protrusion height
  • the surface layer B forming the opposite surface to the surface layer A preferably contains particles, particularly silica particles and/or carbonate particles, from the viewpoint of the slipperiness of the film and the ease with which air can escape.
  • particles particularly silica particles and/or carbonate particles
  • calcium particles are used.
  • the total amount of particles contained in the surface layer B is preferably 5,000 to 15,000 ppm.
  • the arithmetic mean height (Sa) of the film of the surface layer B is preferably in the range of 1 to 40 nm. More preferably, the range is 5 to 35 nm.
  • the total amount of silica particles and/or calcium carbonate particles is 5000 ppm or more and Sa is 1 nm or more, air can be released uniformly when the film is rolled up, resulting in a good rolled shape and good flatness. , it becomes suitable for manufacturing resin sheets. Further, when the total amount of silica particles and/or calcium carbonate particles is 15,000 ppm or less and Sa is 40 nm or less, the lubricant is less likely to aggregate and coarse protrusions are not formed, which is preferable because the quality is stable during resin sheet molding.
  • inert inorganic particles and/or heat-resistant organic particles can be used as the particles contained in the surface layer B.
  • silica particles and/or calcium carbonate particles it is more preferable to use silica particles and/or calcium carbonate particles, but other inorganic particles that can be used include alumina-silica composite oxide particles, hydroxyapatite particles, and the like.
  • the heat-resistant organic particles include crosslinked polyacrylic particles, crosslinked polystyrene particles, and benzoguanamine particles.
  • porous colloidal silica is preferable, and when using calcium carbonate particles, light calcium carbonate whose surface is treated with a polyacrylic acid-based polymer compound is preferable from the viewpoint of preventing the lubricant from falling off. .
  • the average particle diameter of the particles added to the surface layer B is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, particularly preferably 0.5 ⁇ m or more and 1.0 ⁇ m or less. It is preferable that the average particle diameter of the particles is 0.1 ⁇ m or more because the base film has good slipperiness. Further, it is preferable that the average particle diameter is 2.0 ⁇ m or less, since there is no fear that pinholes will be generated in the resin sheet due to the coarse particles of the surface layer B.
  • the surface layer B may contain two or more types of particles made of different materials. Further, particles of the same type but having different average particle diameters may be contained.
  • a coat layer containing particles be provided on the surface layer B to provide slipperiness.
  • This coat layer is not particularly limited, but is preferably provided as an in-line coat applied during the production of the polyester film.
  • the surface of the coat layer has an arithmetic mean height (Sa) for the same reason as the arithmetic mean height (Sa) of the surface layer B described above.
  • the height (Sa) is preferably in the range of 1 to 40 nm. More preferably, the range is 5 to 35 nm.
  • the surface layer A which is the layer on which the resin sheet is provided, in order to prevent particles such as lubricant from being mixed in.
  • the thickness ratio of the surface layer A which is the layer on which the resin sheet is provided, is preferably 20% or more and 50% or less of the total layer thickness of the base film. If it is 20% or more, the effect of particles contained in the surface layer B etc. is less likely to be felt from inside the film, and the arithmetic mean height (Sa) can easily satisfy the above range, which is preferable.
  • the thickness is 50% or less of the total thickness of the base film, the ratio of recycled raw materials used in the surface layer B can be increased, and the environmental load is reduced, which is preferable.
  • the type, amount, particle size, and arithmetic mean height (Sa) of the lubricant contained in the surface layer B satisfy the above ranges.
  • a film may be applied to the surface of surface layer A and/or surface layer B before or after uniaxial stretching during the film forming process.
  • a coating layer may be provided on the substrate, and a corona treatment or the like may be applied.
  • a coat layer is provided on the surface layer A, it is preferable that the coat layer does not substantially contain particles.
  • the present invention has a release layer disposed on at least one side of the base film, for example, between the base film and the resin sheet.
  • the resin constituting the release layer is not particularly limited, and silicone resins, fluororesins, alkyd resins, various waxes, aliphatic olefins, etc. can be used, and each resin can be used alone or in combination of two or more types. .
  • the resin sheet described below contains a crosslinking agent, it is preferable because containing a silicone resin improves mold releasability.
  • the release layer forming composition that forms the release layer contains a silicone resin, a component derived from the silicone resin present in the release layer is transferred to the resin sheet in an appropriate amount.
  • the transition to a resin sheet means a transition within a range that does not impair the mechanical properties, electrical properties, and optical properties required of the resin sheet.
  • a base material and a release layer laminated body may be simply called a release film.
  • the release layer can contain, for example, a silicone resin.
  • Silicone resin is a resin that has a silicone structure in its molecule, and examples include curable silicone, silicone graft resin, and modified silicone resin such as alkyl-modified resin, but from the viewpoint of migration, reactive cured silicone resin It is preferable to use As the reactive cured silicone resin, addition reaction type, condensation reaction type, ultraviolet ray or electron beam curing type, etc. can be used. More preferably, a low-temperature curing addition reaction type that can be processed at low temperatures and an ultraviolet or electron beam curing type are preferred. By using these materials, processing can be performed at low temperatures when coating a polyester film. Therefore, there is less heat damage to the polyester film during processing, a polyester film with high flatness can be obtained, and defects such as pinholes can be reduced even when producing a thin resin sheet.
  • addition reaction type silicone resins include those that are cured by reacting polydimethylsiloxane into which a vinyl group has been introduced into the terminal or side chain with hydrogen siloxane using a platinum catalyst. At this time, it is more preferable to use a resin that can be cured within 30 seconds at 120° C., as this allows processing at low temperatures.
  • Examples include low-temperature addition-curing types manufactured by Dow/Toray (LTC1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTC755, LTC760A, etc.) and thermal UV-curing types (LTC85 1, BY24- 510, BY24-561, BY24-562, etc.), solvent addition + UV curing type (X62-5040, X62-5065, X62-5072T, KS5508, etc.), dual cure curing type (X62-2835, X62- 2834, X62-1980, etc.).
  • condensation reaction silicone resins include those that create a three-dimensional crosslinked structure by condensing polydimethylsiloxane having an OH group at the end and polydimethylsiloxane having an H group at the end using an organotin catalyst. Can be mentioned.
  • UV-curable silicone resins include those that use the same radical reaction as normal silicone rubber crosslinking as the most basic type, those that are photocured by introducing unsaturated groups, and those that are cured by photocuring by introducing unsaturated groups, and those that are made by decomposing onium salts with UV rays. Examples include those that generate a strong acid and use this to cleave the epoxy groups to effect crosslinking, and those that effect crosslinking by addition reaction of thiol to vinylsiloxane. Moreover, an electron beam can also be used instead of the ultraviolet rays. Electron beams have more energy than ultraviolet rays, and it is possible to carry out a crosslinking reaction using radicals without using an initiator as in the case of ultraviolet curing.
  • resins used include UV-curable silicones manufactured by Shin-Etsu Chemical (X62-7028A/B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.), Momentive Performance UV curing silicone manufactured by Materials Co., Ltd. (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.), UV curing silicone manufactured by Arakawa Chemical Co., Ltd. (Silico Lease UV POLY200, POLY215, POLY201, KF-UV2) 65AM etc. ).
  • acrylate-modified or glycidoxy-modified polydimethylsiloxane can also be used.
  • Good mold release performance can also be achieved by mixing these modified polydimethylsiloxanes with polyfunctional acrylate resins, epoxy resins, etc. and using them in the presence of an initiator.
  • Examples of other resins that can be used include stearyl-modified, lauryl-modified alkyd resins and acrylic resins, and alkyd resins, acrylic resins, and olefin resins obtained by reactions with methylated melamine.
  • Examples of the amino alkyd resin obtained by the reaction of methylated melamine include Tesfine 303, Tesfine 305, and Tesfine 314 manufactured by Hitachi Chemical.
  • Examples of the aminoacrylic resin obtained by the reaction of methylated melamine include Tesfine 322 manufactured by Hitachi Chemical.
  • the above resins When the above resins are used in the release layer of the present invention, they may be used alone or in a mixture of two or more types. Further, in order to adjust the release force, it is also possible to mix additives such as light release additives and heavy release additives.
  • Additives such as adhesion improvers and antistatic agents may be added to the release layer of the present invention. Furthermore, in order to improve the adhesion to the base material, it is also preferable to subject the surface of the polyester film to pretreatment such as anchor coating, corona treatment, plasma treatment, atmospheric pressure plasma treatment, etc. before providing the release layer.
  • the thickness of the mold release layer may be set depending on the purpose of use and is not particularly limited, but preferably the thickness of the mold release layer after curing is within a range of 0.005 to 2.0 ⁇ m. good. It is preferable that the thickness of the release layer is 0.005 ⁇ m or more because peeling performance is maintained. Further, it is preferable that the thickness of the release layer is 2.0 ⁇ m or less, since the curing time will not be too long and there will be no risk of uneven thickness of the resin sheet due to deterioration of the flatness of the release film. Furthermore, since the curing time is not too long, there is no risk of the resin constituting the release coating layer coagulating, and there is no risk of forming protrusions, which is preferable because pinhole defects in the resin sheet are less likely to occur.
  • the surface free energy of the release layer provided on the base film of the present invention is 8 mJ/m 2 or more, for example, 10 mJ/m 2 or more, and preferably 12 mJ/m 2 or more. For example, it is 18 mJ/m 2 or more, and may be 20 mJ/m 2 or more. If it is 8 mJ/m 2 or more, it is preferable because repelling and the like are less likely to occur when the solution of the resin sheet is applied.
  • by having the surface free energy of the mold release layer satisfy the above conditions it is possible to provide a well-balanced property of appropriate migration of the mold release layer components to the resin sheet and adhesion to the base film. can.
  • the surface free energy of the release layer provided on the base film of the present invention is preferably 40 mJ/m 2 or less. More preferably, it is 35 mJ/m 2 or less, and even more preferably 30 mJ/m 2 or less. It is preferable that it is 40 mJ/m 2 or less because the molded resin sheet has good releasability.
  • the surface free energy of the release layer when the surface free energy of the mold release layer satisfies the above conditions, it is possible to provide a good balance between appropriate transferability of the mold release layer components to the resin sheet and releasability of the resin sheet.
  • the surface free energy of the release layer means the surface free energy of at least the surface of the release layer that comes into contact with the resin sheet.
  • the water adhesion energy of the surface of the release layer of the present invention in contact with the resin sheet is, for example, 3.0 mJ/m 2 or more, preferably 3.5 mJ/m 2 or more. More preferably, it is 4.0 mJ/m 2 or more, and even more preferably 5.5 mJ/m 2 or more. If it is 3.0 mJ/m 2 or more, it is preferable because swelling of the coated end portion is suppressed when coating the solution of the resin sheet. Suppressing the swelling of the coated edges during coating is preferable because it suppresses ridges when the laminated film is wound into a roll, resulting in a good winding appearance and good flatness of the laminated film. In addition, in this specification, water adhesion energy may be simply described as adhesion energy.
  • the mold release layer In order to improve the water adhesion energy on the surface of the mold release layer, it can be achieved by adding additives to the mold release layer or adjusting the polymer composition.
  • additives for example, in the case of silicone resin, a siloxane unit having a phenyl group on the side chain is introduced into the polydimethylsiloxane skeleton, or a silicone resin with T units (trifunctional) or Q units (tetrafunctional) is added. This can be improved.
  • the composition of the silicone resin can also be changed by changing the composition of the silicone resin as a method other than the above.
  • addition reaction-based silicone resins can be cured by heating polydimethylsiloxane and hydrogen siloxane, which have vinyl groups introduced into their terminals or side chains, under a platinum catalyst.
  • the water adhesion energy can also be changed by changing the molar amount of Si-H groups in hydrogensiloxane.
  • the water adhesion energy tends to be higher when there is more Si-H than Si-Vy, and the ratio of Si-H/Si-Vi is preferably 1.0 or more, more preferably 1.5 or more. More preferably 2.0 or more.
  • the release layer of the present invention preferably has an arithmetic mean height (Sa) of not only the polyester base material but also the release layer of 20 nm or less. Furthermore, it is particularly preferable that the arithmetic mean height (Sa) is 10 nm or less. When Sa is 20 nm or less, pinholes and local thickness unevenness are less likely to occur during molding of the resin sheet, which is preferable. It can be said that the smaller the arithmetic mean height (Sa) of the release layer is, the more preferable it is, but it may be 0.1 nm or more.
  • the maximum protrusion height (P) of the release layer is, for example, 500 nm or less, preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, for example, 85 nm or less, and 50 nm or less. Particularly preferred. If the maximum protrusion height (P) is 500 nm or less, defects such as pinholes and local thinning will not occur during the formation of the resin sheet, and the yield will be good, which is preferable.
  • the method of forming the mold release layer is not particularly limited, and a coating liquid in which a mold release resin is dissolved or dispersed is spread by coating on one side of a polyester film as a base material, and a solvent etc. After removing by drying, heat drying, heat curing, or ultraviolet curing is used.
  • Any known coating method can be applied to the above-mentioned release layer, such as roll coating methods such as gravure coating method and reverse coating method, bar coating method such as wire bar coating method, die coating method, spray coating method, and air coating method. Conventionally known methods such as a knife coating method can be used.
  • the drying temperature during solvent drying and thermosetting is preferably 180°C or lower, more preferably 160°C or lower, and 140°C or lower. is more preferable, and most preferably 120° C. or lower.
  • the heating time is preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 10 seconds or less.
  • the temperature is 180° C. or lower, the flatness of the film is maintained and there is little risk of causing thickness unevenness of the resin sheet, which is preferable. It is particularly preferable that the temperature is 120° C. or lower, since the film can be processed without impairing its flatness and the possibility of causing thickness unevenness of the resin sheet is further reduced.
  • the lower limit of the drying temperature is not particularly limited, it is preferably 60°C or higher. It is preferable that the temperature is 60° C. or higher because a release film can be obtained without any solvent remaining in the release layer.
  • the drying temperature during solvent drying and heat curing is preferably 120°C or lower, more preferably 100°C or lower, and 90°C or lower. is the most preferred.
  • the heating time is preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 10 seconds or less.
  • the temperature is 120° C. or lower, the flatness of the film is maintained and there is little risk of causing thickness unevenness of the resin sheet, which is preferable. It is particularly preferable that the temperature is 90° C. or lower, since the film can be processed without impairing its flatness and the possibility of causing thickness unevenness of the resin sheet is further reduced.
  • the lower limit of the drying temperature is not particularly limited, it is preferably 60°C or higher. It is preferable that the temperature is 60° C. or higher because a release film can be obtained without any solvent remaining in the release layer.
  • an ultraviolet curable material for the release layer
  • the active energy ray to be used known techniques such as ultraviolet rays and electron beams can be used, and it is preferable to use ultraviolet rays.
  • the cumulative amount of light when using ultraviolet light can be expressed as the product of illuminance and irradiation time. For example, it is preferably 10 to 500 mJ/cm 2 . It is preferable to set it to the lower limit or more because the release layer can be sufficiently cured. By setting it below the above upper limit, thermal damage to the film due to heat during irradiation can be suppressed and the smoothness of the surface of the release layer can be maintained, which is preferable.
  • the laminated film of the present invention has a resin sheet disposed on the surface of the release layer opposite to the base material.
  • the resin sheet to be laminated on the release film of the present invention is a cured resin sheet-forming composition containing at least a resin component (A) and a crosslinking agent (B).
  • the resin sheet of the present invention can be produced under specific conditions described below, for example, by forming it from the resin sheet forming composition according to the present invention, in a state in which the resin component (A) and the crosslinking agent (B) are phase-separated. This enables the resin sheet to be cured, form appropriate irregularities on the surface of the resin sheet, and exhibit the slipperiness of the resin sheet without containing particles or the like.
  • the combined mass ratio of the resin component (A) and the crosslinking agent (B) preferably accounts for 80% by mass or more of the solid content of the entire resin sheet, more preferably 90% by mass or more, and even more preferably 95% by mass or more. . It is preferable that the content is 80% by mass or more because physical properties such as strength and heat resistance of the resin sheet are improved.
  • the blending ratio of the crosslinking agent (B) is 10% by mass or more, it is preferable because the unevenness after phase separation tends to increase and the slipperiness improves. If the blending ratio of the crosslinking agent (B) is 50% by mass or less, the film strength of the resin sheet will not decrease and the sheet will be easy to handle, which is preferable. Blocking with the back side can also be prevented.
  • the proportion of the crosslinking agent (B) contained in the resin sheet to the entire resin sheet is 10% by mass or more and 50% by mass or less.
  • the proportion of the crosslinking agent (B) contained in the resin sheet in the entire resin sheet is 10% by mass or more, for example, 10% by mass or more when the total solid content of the resin sheet is 100% by mass. It is less than 50% by mass, for example, 15% by mass or more and 45% by mass or less.
  • the resin component (A) is not particularly limited, and known resins can be used. For example, epoxy resins, phenoxy resins, polyester resins, urethane resins, fluorine resins, acrylic resins, olefin resins, imide resins, sulfone resins, etc. can be used, and even if only one type is used. Two or more types may be used in combination.
  • the weight average molecular weight (Mw) of the resin component (A) used in the present invention is 10,000 or more, preferably 10,000 or more and 200,000 or less, and more preferably 30,000 or more and 100,000 or less. If it is 10,000 or more, the strength of the resin sheet is strong and the handleability is good, so it is preferable.
  • the viscosity of the solution decreases and productivity becomes good when performing solution film formation, which is preferable.
  • the method for measuring the weight average molecular weight (Mw) is not particularly limited, but it can be measured using GPC or the like.
  • the crosslinking agent (B) is not particularly limited, and known crosslinking agents can be used.
  • crosslinking agents such as isocyanate, melamine, carbodiimide, and oxazoline can be used, and one type or a mixture of two or more types may be used. It is preferable that it reacts with the functional group contained in the resin component (A).
  • the crosslinking agent (B) contained in the resin sheet forming composition is preferably liquid at 30°C.
  • the liquid may be any fluid as long as it has fluidity, for example, a viscosity of 10,000 mPa ⁇ s or less. Being liquid at 30° C. is preferable because phase separation from the resin component (A) can be effectively promoted during drying of solution casting of the resin sheet, and surface irregularities of the resin sheet can be easily formed.
  • the resin sheet may contain additives in addition to the resin component (A) and the crosslinking agent (B) as long as the above ranges are satisfied.
  • the resin sheet does not substantially contain particles. Since the resin sheet according to the present invention does not substantially contain particles, it has the effect of increasing the transparency of the molded resin sheet for optical applications, for example, and for electronic applications such as dielectric sheets used in film capacitors. It is preferable for parts because it is easy to obtain effects such as improved electrical characteristics.
  • the resin sheet can have a haze of 2% or less. Further, the haze may be 1% or less. In one embodiment, the resin sheet has a haze of 0.1% or more.
  • the resin sheet in the case of an electronic component such as a film capacitor, can have a dielectric breakdown voltage of 200 V/ ⁇ m or more. Further, the dielectric breakdown voltage may be 300 V/ ⁇ m or more. In one embodiment, the breakdown voltage is 500V/ ⁇ m or less.
  • the details of the technical feature that "the resin sheet does not substantially contain particles" can be interpreted by applying the content described above regarding the base material to the resin sheet.
  • the additives to be mixed in the resin sheet in addition to the resin component (A) and the crosslinking agent (B) are preferably those that have good compatibility with the resin component (A) and can react with the crosslinking agent (B).
  • polyurethane, polyester, polyketone, polyol, polyarylate, phenoxy, epoxy, etc. are preferred.
  • polyol-based resins are more preferred.
  • the resin sheet of the present invention does not substantially contain particles, it has good slip properties because of the presence of minute irregularities on the surface due to phase separation of the resin component (A) and the crosslinking agent (B).
  • the static friction coefficient ( ⁇ s) of the resin sheet peeled from the base film is preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.8 or less. It is preferable that the static friction coefficient is 1.5 or less because when used as a resin sheet for optical applications or electronic parts applications, the resin sheet has good winding properties, running properties, etc., and is easy to handle.
  • the static friction coefficient of the resin sheet may be 0.1 or more. In one embodiment, in FIG.
  • the static friction coefficient is measured by overlapping the surface (1) of the resin sheet opposite to the release layer, indicated by the reference numeral 13, and the surface (2) of the resin sheet, indicated by the reference numeral 14. is 1.5 or less.
  • the static friction coefficient measured under the above conditions is more preferably 1.0 or less, and even more preferably 0.8 or less. Further, the static friction coefficient may be 0.1 or more. As described above, since the static friction coefficient measured by overlapping both sides of the resin sheet is within the above range, the resin sheet of the present invention can achieve both high smoothness and excellent winding and running properties. can.
  • the arithmetic mean roughness (Sa) of the surface (1) of the resin sheet of the laminated film of the present invention is 2 nm or more and 30 nm or less;
  • the thickness is more preferably 20 nm or less, and even more preferably 2.5 nm or more and 15 nm or less.
  • the thickness is 2 nm or more, the resin sheet has good slipperiness, which is preferable.
  • the thickness is 30 nm or less, even when the resin sheet is peeled off from the laminated film and only the resin sheet is wound up into a roll, there is less concern that defects such as pinholes will occur, which is preferable.
  • the maximum cross-sectional height (St) of the surface (1) of the resin sheet of the laminated film of the present invention is 80 nm or more and 1000 nm or less, and 100 nm or more, The thickness is more preferably 600 nm or less, and even more preferably 150 nm or more and 500 nm or less. When it is 80 nm or more, the resin sheet has good slipperiness, which is preferable. If it is 1000 nm or less, even when the resin sheet is peeled off from the laminated film and only the resin sheet is wound up into a roll, there is less concern that defects such as pinholes will occur, which is preferable. Note that the maximum cross-sectional height (St) is the sum of the absolute values of the maximum protrusion height (P) and the maximum valley depth (V).
  • the maximum protrusion height (P) of the surface (1) of the resin sheet of the laminated film of the present invention is preferably 500 nm or less, and preferably 250 nm or less. is more preferred, further preferably 200 nm or less, may be 185 nm or less, for example 150 nm or less, and particularly preferably 135 nm or less. For example, it may be 100 nm or less. If the maximum protrusion height (P) on the surface (1) of the resin sheet is 500 nm or less, defects such as pinholes will occur even if the resin sheet is peeled from the laminated film and only the resin sheet is rolled up. It is preferable that there is no such thing. Although it can be said that the smaller the maximum protrusion height P is, the more preferable it is, it may be 1 nm or more, 3 nm or more, for example, 35 nm or more.
  • the maximum valley depth (V) of the surface (1) of the resin sheet of the laminated film is preferably 45 nm or more and 350 nm or less, for example, 45 nm or more and 300 nm or less, and preferably 45 nm or more and 250 nm or less.
  • the resin sheet of the present invention does not need to contain substantially any particles. This is because the surface has minute irregularities caused by phase separation of the resin component (A) and the crosslinking agent (B), so that it can have good slipperiness.
  • the surface free energy of the surface (2) of the resin sheet of the laminated film of the present invention is 45 mJ/m 2 or less. More preferably it is 42 mJ/m 2 or less, and still more preferably 38 mJ/m 2 or less. When it is 45 mJ/m 2 or less, the slipperiness of the resin sheet can be improved. Moreover, it can exhibit physical properties required in optical applications and electronic component applications, such as optical properties and electrical properties, without impairing them.
  • the surface free energy of the surface (2) of the resin sheet in contact with the mold release layer is reduced by at least a portion of the components of the mold release layer migrating to the surface of the resin sheet. It is estimated that it is possible to lead to 45 mJ/m 2 or less. Furthermore, in the present invention, it is assumed that at least a portion of the components of the release layer migrate to the surface of the resin sheet, and furthermore, electrical properties such as dielectric breakdown voltage are not impaired. Furthermore, since the surface free energy can be guided to a predetermined condition, the coefficient of friction can be reduced.
  • the surface free energy of the surface (2) of the resin sheet in contact with the release layer is 1 mJ/m 2 or more, for example, 10 mJ/m 2 or more, and may be 15 mJ/m 2 or more. Further, it may be 20 mJ/m 2 or more.
  • the surface free energy is within this range, electrical properties such as dielectric breakdown voltage are not impaired even though at least a part of the components of the release layer are transferred to the surface of the resin sheet. Therefore, in the present invention, when the surface free energy of the surface (2) of the resin sheet in contact with the release layer satisfies specific conditions, it is possible to exhibit good slipperiness and electrical properties in a well-balanced manner.
  • the surface free energy of the surface (2) on the release layer side of the resin sheet is 45 mJ/m 2 or less, as measured after peeling the resin sheet from the laminated film.
  • the measurement of surface free energy in this embodiment is performed after peeling the resin sheet from the release layer in the laminated film, and it is desirable that the time difference between peeling and measurement be as short as possible.
  • the surface free energy of the resin sheet is measured within 20 minutes after peeling the resin sheet from the release layer.
  • aging can be performed at 40° C. for 2 days in a state where the release layer and the resin sheet are in contact with each other, and then evaluation can be performed.
  • the arithmetic mean roughness (Sa) of the surface (2) of the resin sheet of the laminated film of the present invention is preferably 10 nm or less, more preferably 8 nm or less. , 5 nm or less is more preferable. If the thickness is 10 nm or less, even when the resin sheet is peeled off from the laminated film and only the resin sheet is wound up into a roll, there is less concern that defects such as pinholes will occur, which is preferable.
  • the film thickness (t1) of the resin sheet of the present invention is 1 ⁇ m or more and 20 ⁇ m or less. More preferably, it is 1 ⁇ m or more and 10 ⁇ m or less, and even more preferably 2 ⁇ m or more and 8 ⁇ m or less. If the thickness (t1) of the resin sheet is 1 ⁇ m or more, it is preferable because it is difficult to tear and can be easily handled even after being peeled off from the base film. If the film thickness (t1) of the resin sheet is 20 ⁇ m or less, it is preferable because the wet coating film thickness does not become too thick during solution film forming and molding is easy.
  • the film thickness (t1) of the resin sheet is not particularly limited and can be measured by a known method.
  • a contact type film thickness meter, an optical interference type film thickness meter, or a cross section can be observed and measured using a scanning electron microscope, a transmission electron microscope, or the like.
  • a coating liquid containing at least the above-mentioned resin component (A) and crosslinking agent (B) and dissolved or dispersed in an organic solvent, water, etc. i.e., resin sheet formation
  • a coating liquid containing at least the above-mentioned resin component (A) and crosslinking agent (B) and dissolved or dispersed in an organic solvent, water, etc. i.e., resin sheet formation
  • a solution casting method i.e., resin sheet formation
  • conventionally known methods such as a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar coating method, a die coating method, a spray coating method, an air knife coating method, etc. can be used.
  • the coating liquid After applying the coating liquid to the release layer, it is preferable to include a heating step in order to dry and harden the solvent.
  • the heating method is not particularly limited, but the laminated film after coating can be heated using hot air, infrared rays, or the like.
  • the laminated film of the present invention is preferably coated and dried in a roll-to-roll manner, and is particularly preferably dried using hot air in a drying oven such as a floating method or a roll support method.
  • the maximum temperature of the drying oven is preferably 60°C or more and 160°C or less, more preferably 70°C or more and 140°C or less, and even more preferably 70°C or more and 130°C or less. If it is 60° C. or higher, there is little residual solvent in the resin sheet after drying, and there is no fear that the performance of the resin sheet (for example, electrical properties if used as a dielectric layer) will deteriorate, so it is preferable. If it is 160° C. or lower, there is no concern that the laminated film will wrinkle due to heat, so it is preferable.
  • the temperature is higher than 160°C, there is a concern that the phase separation between the resin component and the crosslinking agent in the resin sheet will proceed too much and the crosslinking density of the resin sheet will decrease, so it is preferable to keep the temperature at 160°C or lower.
  • the time from applying the coating liquid to the base film to entering the drying oven is preferably within 5 seconds, more preferably within 3 seconds, and even more preferably within 2 seconds. If it is within 5 seconds, the phase separation between the resin component and the crosslinking agent in the coating liquid will not proceed too much, and there will be no concern that the crosslinking density of the resin sheet will decrease, which is preferable.
  • the time for heating at the maximum temperature in a drying oven is preferably 1 second or more, and preferably 2 seconds or more. It is preferable that the time is 1 second or more because the reaction of the crosslinking agent proceeds.
  • the upper limit of the heating time is preferably within 60 seconds, more preferably within 40 seconds, and even more preferably within 20 seconds. If the heating time is within 60 seconds, it is preferable because segregation of the crosslinking agent onto the surface of the resin sheet can be prevented from progressing excessively, and the performance of the resin sheet will not be deteriorated.
  • the phase separation of the resin component (A) and the crosslinking agent (B) can proceed appropriately, and the arithmetic mean roughness (Sa) of the resin sheet surface (1) can be improved.
  • the maximum cross-sectional height (St) can be controlled within the above range, and the resin sheet can exhibit good sliding properties without adding particles to the resin sheet.
  • the laminated film of the present invention is used after the resin sheet is peeled off from the release layer laminated on the base film in subsequent steps. Therefore, it is preferable that the peeling force from the release layer laminated on the base film is 800 mN/25 mm width or less because the resin sheet can be peeled off without breaking. More preferably it is 500 mN/25 mm width or less, still more preferably 300 mN/25 mm width or less, and even more preferably 200 mN/25 mm width or less. Since the peeling force differs depending on the laminated resin sheets, it can be adjusted by the type of release layer laminated on the base film.
  • the contact angle data of water and diiodomethane obtained by the above method were calculated using the "Owens and Wendt" theory, and the dispersion component ⁇ d of the surface free energy of the release film was calculated, and the component ⁇ h was calculated based on the hydrogen bond and dipole-dipole interaction. was determined, and the sum of each component was defined as the surface free energy ⁇ s.
  • This calculation was performed using analysis software included in the contact angle meter software (FAMAS).
  • the surface free energy of the surface (2) of the resin sheet on the mold release layer side was measured within 20 minutes after the resin sheet was peeled from the mold release layer.
  • the following resin coating liquid was applied onto the release surface of the release film using a wire bar so that the resin sheet thickness after drying was 3 ⁇ m, and dried in a hot air oven at 120° C. for 30 seconds.
  • the coating width (W 1 ) immediately after coating the resin solution and the width (W 2 ) of the resin film after drying were measured.
  • one half of the difference between the coating width (W 1 ) and the width of the resin film (W 2 ) was defined as the edge repellency width.
  • the wettability was evaluated based on the measured edge repellency width according to the following criteria.
  • End repellent width [mm] (W1-W2)/2 (resin solution) Methyl ethyl ketone 41.3 parts by mass Tetrahydrofuran 22.5 parts by mass PKHB solution (solid content 40% by mass) 30.6 parts by mass (Phenoxy resin manufactured by Gabriel Phenoxies, Mw 32000) *The solution was prepared by dissolving phenoxy resin in tetrahydrofuran.
  • the cut laminated film was embedded in resin and cut into ultrathin sections using an ultramicrotome. Thereafter, direct observation was performed at a magnification of 20,000 times using a JEOL JEM2100 transmission electron microscope, and the thickness of each layer of the laminated film was measured from the observed TEM image.
  • the laminated film was cut into strips with a width of 25 mm and a length of 150 mm, the base film and one end of the release layer were fixed, one end of the resin sheet was supported, and the resin sheet side was pulled at a speed of 300 mm/min.
  • the peel strength was measured.
  • a tensile tester (“AUTOGRAPH AG-X” manufactured by Shimadzu Corporation) was used for the measurement. The average value of 5 measurements was used as the measured value.
  • the peelability was evaluated based on the measured peeling force according to the following criteria. ⁇ : It was possible to peel off with a low peeling force of 100 mN/25 mm width or less, and even a thin film could be peeled off without tearing.
  • ⁇ It was possible to peel off with a peeling force of 300 mN/25 mm width or less and greater than 100 mN/25 mm width. Ta. ⁇ : Peeling force was greater than 300 mN/25 mm width and could be peeled off with less than 800 mN/25 mm width. In parts where the film thickness was extremely thin, some parts were broken. ⁇ : Can not be peeled off.
  • the static friction coefficient of the resin sheet was measured as follows, and the slipperiness was evaluated.
  • the resin sheet was peeled off from the laminated film and fixed to the bottom of a metal rectangular parallelepiped weighing 1.4 kg so that the surface (2) of the resin sheet was facing up.
  • the resin sheet was fixed with adhesive tape onto a flat metal plate with the surface (1) facing up.
  • a metallic rectangular parallelepiped was placed so that surfaces (1) and (2) were in contact with each other, and the coefficient of static friction was measured at a pulling speed of 200 mm/min at 23° C. and 65% RH.
  • the slipperiness was judged based on the following criteria. ⁇ : 0.1 ⁇ s ⁇ 0.8 ⁇ : 0.8 ⁇ s ⁇ 1.5 ⁇ : Over 1.5 or the friction coefficient is too high to measure
  • Dielectric breakdown voltage (BDV value) is 300V/ ⁇ m or more
  • Dielectric breakdown voltage is 200V/ ⁇ m or more
  • Dielectric breakdown voltage is less than 200V/ ⁇ m
  • TPA terephthalic acid
  • EG ethylene glycol
  • antimony trioxide is set at an amount such that Sb atoms are 160 ppm relative to the produced PET, and these slurries are converted into esters.
  • the mixture was continuously supplied to the first esterification reactor of the esterification reactor, and reacted at 255°C for an average residence time of 4 hours at normal pressure.
  • the reaction product in the first esterification reactor is continuously taken out of the system and supplied to the second esterification reactor, and the reaction product is distilled from the first esterification reactor into the second esterification reactor.
  • an EG solution containing magnesium acetate tetrahydrate in an amount such that Mg atoms are 65 ppm relative to the produced PET, and 40 ppm P atoms relative to the produced PET is supplied.
  • the esterification reaction product produced in the third esterification reactor was continuously fed to a three-stage continuous polycondensation reactor to perform polycondensation, and stainless steel fibers with a 95% cut diameter of 20 ⁇ m were sintered. After filtration with a filter, ultrafiltration was performed and extruded into water, and after cooling, it was cut into chips to obtain PET chips with an intrinsic viscosity of 0.60 dl/g (hereinafter abbreviated as PET (I)). .
  • PET (I) intrinsic viscosity of 0.60 dl/g
  • PET polyethylene terephthalate pellets
  • PET polyethylene terephthalate pellets
  • type and content of PET (I) particles were changed to 0.75% by mass of synthetic calcium carbonate with an average particle size of 0.9 ⁇ m, to which 1% by mass of ammonium salt of polyacrylic acid was attached per calcium carbonate.
  • a PET chip was obtained in the same manner as PET (I) (hereinafter referred to as PET (III) ).
  • the lubricant content in the PET chip was 0.75% by mass.
  • PET chips were melted at 285°C, melted at 290°C by a separate melt extruder extruder, and filtered with sintered stainless steel fibers with a 95% cut diameter of 15 ⁇ m and a filter with a 95% cut diameter of 15 ⁇ m.
  • Two stages of filtration are performed using a filter made of sintered stainless steel particles of 15 ⁇ m, which are combined in a feed block, and PET (I) is layered as surface layer B, and PET (II) is layered as surface layer A.
  • the unstretched polyethylene terephthalate sheet with an intrinsic viscosity of 0.59 dl/g was extruded (casted) into a sheet shape at a speed of 45 m/min, and electrostatically adhered and cooled on a casting drum at 30°C using the electrostatic adhesion method. Obtained.
  • this unstretched sheet was heated with an infrared heater, and then stretched 3.5 times in the machine direction at a roll temperature of 80° C. using a speed difference between the rolls. Thereafter, it was introduced into a tenter and stretched 4.2 times in the transverse direction at 140°C.
  • a biaxially stretched polyethylene terephthalate film with a thickness of 12 ⁇ m was created by adjusting the thickness by changing the casting speed without changing the layer structure and stretching conditions similar to those of base film A base film X3 was obtained by providing a mold layer.
  • the Sa of the surface layer A of the obtained film X3 was 3 nm, and the Sa of the surface layer B was 29 nm.
  • A4100 Cosmoshine (registered trademark), manufactured by Toyobo Co., Ltd.) having a thickness of 25 ⁇ m was used.
  • A4100 does not substantially contain particles in the film, and has a structure in which a coating layer containing particles is provided only on the surface layer B side by inline coating.
  • the Sa of the surface layer A of the base film X4 was 1 nm, and the Sa of the surface layer B was 2 nm.
  • E5101 Toyobo Ester (registered trademark) film, manufactured by Toyobo Co., Ltd.) with a release layer similar to X2 on the surface layer A was used.
  • E5101 has a structure in which particles are contained in the surface layers A and B of the film.
  • the Sa of the surface layer A of the base film X5 was 25 nm, and the Sa of the surface layer B was 25 nm.
  • E5101 Toyobo Ester (registered trademark) film, manufactured by Toyobo Co., Ltd.) with a thickness of 25 ⁇ m
  • the following non-silicone release coating liquid Y5 was applied by reverse gravure coating to a wet film thickness of 5 ⁇ m. It was coated and dried and cured at 170° C. for 30 seconds in a hot air drying oven to obtain a base film X9 with a release layer. Sa on the surface of the release layer was 23 nm.
  • E5101 has a structure in which particles are contained in the surface layer A and the surface layer B of the film.
  • Example 1 The resin solution Z1 was coated on the surface layer A of the base film X2, that is, on the release layer, using a reverse gravure coating method so that the thickness of the dried resin sheet was 3 ⁇ m, and then dried in a hot air drying oven. A resin sheet was formed by drying at 120° C. for 10 seconds to create a laminated film. (At this time, it took 2 seconds to enter the drying oven after coating). Details are shown in Tables 1 and 2.
  • Example 2 A laminated film was produced in the same manner as in Example 1, except that the base film and release layer were changed to those listed in Table 1.
  • Example 5 A laminated film was produced in the same manner as in Example 1, except that the resin solution Z2 was used to change the type of crosslinking agent.
  • Resin solution Z2 Methyl ethyl ketone 41.3 parts by mass Tetrahydrofuran 22.5 parts by mass PKHB solution (solid content 40% by mass) 30.6 parts by mass (Phenoxy resin manufactured by Gabriel Phenoxies, Mw 32000) *The solution was prepared by dissolving phenoxy resin in tetrahydrofuran Millionate MR-400 5.3 parts by mass (manufactured by Tosoh Corporation, isocyanate crosslinking agent, viscosity 600mPa ⁇ s, solid content 99% by mass) BYK-370 0.4 parts by mass (manufactured by BYK-Chemie Japan, silicone surfactant)
  • Example 6 A laminated film was produced in the same manner as in Example 1, except that the type of crosslinking agent was changed to resin solution Z3.
  • resin solution Z3 Methyl ethyl ketone 41.3 parts by mass Tetrahydrofuran 22.5 parts by mass PKHB solution (solid content 40% by mass) 30.6 parts by mass (Phenoxy resin manufactured by Gabriel Phenoxies, Mw 32000) *The solution was prepared by dissolving phenoxy resin in tetrahydrofuran.
  • Example 7 A laminated film was produced in the same manner as in Example 1, except that resin solution Z4 was used to change the ratio of resin and crosslinking agent.
  • resin solution Z4 Methyl ethyl ketone 41.3 parts by mass Tetrahydrofuran 19.9 parts by mass PKHB solution (solid content 40% by mass) 35.0 parts by mass (Phenoxy resin manufactured by Gabriel Phenoxies, Mw 32000) *The solution was prepared by dissolving phenoxy resin in tetrahydrofuran.
  • Example 8 A laminated film was produced in the same manner as in Example 1, except that resin solution Z5 was used to change the ratio of resin and crosslinking agent.
  • resin solution Z5 Methyl ethyl ketone 41.3 parts by mass Tetrahydrofuran 17.3 parts by mass PKHB solution (solid content 40% by mass) 39.4 parts by mass (Phenoxy resin manufactured by Gabriel Phenoxies, Mw 32000) *The solution was prepared by dissolving phenoxy resin in tetrahydrofuran Millionate MR-200 1.8 parts by mass (manufactured by Tosoh Corporation, isocyanate crosslinking agent, viscosity 200 mPa ⁇ s, solid content 99 mass%) BYK-370 0.4 parts by mass (manufactured by BYK-Chemie Japan, silicone surfactant)
  • Example 9 A laminated film was produced in the same manner as in Example 1, except that the base film with a release layer shown in Table 1 was used.
  • Example 12-13 A laminated film was produced in the same manner as in Example 1, except that the drying temperature of the resin sheet was changed to the temperature listed in Table 1.
  • Example 1 A laminated film was produced in the same manner as in Example 1, except that the base film was changed to X1 without a release layer.
  • the base film used in each example was used after processing the release layer and aging at 40° C. for 3 days. Moreover, the obtained laminated film was evaluated after aging at 40° C. for 2 days.
  • Example 14 A laminated film was produced in the same manner as in Example 6, except that the resin solution was changed to Z8 in order to change the type of resin.
  • (Resin solution Z8) Methyl ethyl ketone 41.3 parts by mass Tetrahydrofuran 12.3 parts by mass Vylon 200 solution (solid content 30% by mass) 40.8 parts by mass (Toyobo polyester resin, Mn 17000, MEK/toluene solution) *The solution was prepared by dissolving polyester resin in MEK/toluene solution Millionate MTL 5.3 parts by mass (manufactured by Tosoh Corporation, isocyanate crosslinking agent, viscosity 50 mPa ⁇ s, solid content 99 mass%) BYK-370 0.4 parts by mass (manufactured by BYK-Chemie Japan, silicone surfactant) Note that the surface free energy of the resin sheet at the surface (2) on the release layer side was 35.2 mJ/m 2 .
  • Example 15 A laminated film was produced in the same manner as in Example 6, except that resin solution Z9 was used to change the types of resin and crosslinking agent.
  • resin solution Z9 Methyl ethyl ketone 41.3 parts by mass Tetrahydrofuran 7.4 parts by mass UR-4800 (solid content 32% by mass) 49.2 parts by mass (Toyobo Co., Ltd.
  • polyester urethane resin Mn25000, MEK/toluene dissolved product
  • Nikalac MW-30 1.8 parts by mass
  • BYK-370 0.4 parts by mass (manufactured by BYK-Chemie Japan, silicone surfactant)
  • the surface free energy of the resin sheet at the surface (2) on the release layer side was 35.2 mJ/m 2 .
  • compositions, evaluation results, etc. of Examples and Comparative Examples are shown in Table 1A, Table 1B, Table 2A, and Table 2B.
  • the laminated sheet of the present invention obtained in the Examples is a resin sheet that can improve transparency in optical applications, for example, and can also provide a resin sheet that exhibits high smoothness. Moreover, it is possible to achieve both high smoothness and high slipperiness, and for example, it is possible to suppress scratches during the conveyance process, etc., and it is possible to avoid a decrease in yield. Furthermore, for electronic component applications such as film capacitor applications, a resin sheet that exhibits high smoothness can be provided, and the resin sheet can improve electrical properties such as dielectric breakdown voltage.
  • the resin sheet obtained by the present invention does not substantially contain particles, and can avoid insufficient transparency such as increased internal haze. Further, it is possible to avoid the problem of non-uniformity in the amount of particles transferred to the resin sheet, and it is possible to exhibit good slipperiness. Furthermore, it is presumed that at least a part of the components of the release layer can be transferred to the surface of the resin sheet, and the present invention can exhibit good slipperiness and electrical properties in a well-balanced manner.
  • Comparative Example 1 did not have the release layer according to the present invention, the releasability of the resin sheet was extremely poor, and the resin sheet could not be evaluated.
  • Comparative Example 2 since the resin sheet forming composition did not contain a crosslinking agent, the slipperiness of the resin sheet was particularly poor.
  • Reference Example 3 the surface free energy of the surface (2) on the release layer side of the resin sheet is slightly outside the range of the present invention, and the slipperiness of the resin sheet and the electrical properties of the resin sheet are inferior to those of the present invention. This was the result. Furthermore, it was not possible to measure water adhesion energy. Furthermore, the peeling force tended to be high.
  • the present invention relates to a laminated film in which resin sheets are laminated.
  • the present invention relates to a laminated film in which resin sheets are laminated for use in electronic components and optical applications.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un film stratifié capable de fournir une feuille de résine associant un lissé élevé avec une glissance satisfaisante. La solution selon la présente invention porte sur un film stratifié comprenant un film de base à base de polyester, une couche anti-adhésive disposée sur au moins une surface du film de base, et une feuille de résine disposée sur la surface de la couche anti-adhésive sur le côté opposé à la base, le film stratifié satisfaisant ce qui suit : la feuille de résine est une feuille obtenue par durcissement d'une composition de formation de feuille de résine comprenant au moins un composant de résine (A) et un agent de réticulation (B) ; la feuille de résine ne contient sensiblement pas de particules ; la feuille de résine présente une épaisseur de film (t1) de 1 à 20 µm ; la feuille de résine présente une surface (1) ayant une hauteur moyenne arithmétique (Sa) de 2 à 30 nm ; la surface côté couche anti-adhésive (2) de la feuille de résine, lorsqu'elle est examinée après que la feuille de résine a été retirée du film stratifié, présente une énergie libre de surface inférieure ou égale à 45 mJ/m2 ; et le coefficient de frottement statique entre la surface (1) sur le côté inverse de la feuille de résine à partir de la surface de couche anti-adhésive et la surface côté couche anti-adhésive (2) de la feuille de résine est inférieure ou égale à 1,5.
PCT/JP2023/026229 2022-07-20 2023-07-18 Film stratifié et procédé de production de film stratifié WO2024019039A1 (fr)

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JP2022115569 2022-07-20

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009013384A (ja) * 2007-07-09 2009-01-22 Nippon Paint Co Ltd 易滑性アンチブロッキング光硬化性樹脂組成物、それを基材上に被覆硬化したアンチブロッキング性構造体およびその製法
JP2012229399A (ja) * 2011-04-25 2012-11-22 Toray Advanced Materials Korea Inc 透明プラスチック基板用フェノキシ樹脂組成物及びそれを用いた透明プラスチック基板素材
WO2021005823A1 (fr) * 2019-07-10 2021-01-14 株式会社村田製作所 Condensateur à film et film pour condensateur à film
JP2022025703A (ja) * 2020-07-29 2022-02-10 東洋紡株式会社 積層フィルム
WO2022163569A1 (fr) * 2021-01-26 2022-08-04 東洋紡株式会社 Film stratifié et procédé de fabrication de film stratifié
WO2022186184A1 (fr) * 2021-03-02 2022-09-09 東洋紡株式会社 Film stratifié et procédé de fabrication de film stratifié
JP2023111664A (ja) * 2022-01-31 2023-08-10 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2023111662A (ja) * 2022-01-31 2023-08-10 三菱ケミカル株式会社 ポリエステルフィルムロール

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009013384A (ja) * 2007-07-09 2009-01-22 Nippon Paint Co Ltd 易滑性アンチブロッキング光硬化性樹脂組成物、それを基材上に被覆硬化したアンチブロッキング性構造体およびその製法
JP2012229399A (ja) * 2011-04-25 2012-11-22 Toray Advanced Materials Korea Inc 透明プラスチック基板用フェノキシ樹脂組成物及びそれを用いた透明プラスチック基板素材
WO2021005823A1 (fr) * 2019-07-10 2021-01-14 株式会社村田製作所 Condensateur à film et film pour condensateur à film
JP2022025703A (ja) * 2020-07-29 2022-02-10 東洋紡株式会社 積層フィルム
WO2022163569A1 (fr) * 2021-01-26 2022-08-04 東洋紡株式会社 Film stratifié et procédé de fabrication de film stratifié
WO2022186184A1 (fr) * 2021-03-02 2022-09-09 東洋紡株式会社 Film stratifié et procédé de fabrication de film stratifié
JP2023111664A (ja) * 2022-01-31 2023-08-10 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2023111662A (ja) * 2022-01-31 2023-08-10 三菱ケミカル株式会社 ポリエステルフィルムロール

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