WO2023047936A1 - Film de polyester à orientation biaxiale - Google Patents

Film de polyester à orientation biaxiale Download PDF

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Publication number
WO2023047936A1
WO2023047936A1 PCT/JP2022/033366 JP2022033366W WO2023047936A1 WO 2023047936 A1 WO2023047936 A1 WO 2023047936A1 JP 2022033366 W JP2022033366 W JP 2022033366W WO 2023047936 A1 WO2023047936 A1 WO 2023047936A1
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WIPO (PCT)
Prior art keywords
layer
biaxially oriented
oriented polyester
polyester film
film
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PCT/JP2022/033366
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English (en)
Japanese (ja)
Inventor
千代敏弘
東大路卓司
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東レ株式会社
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Priority to CN202280064281.XA priority Critical patent/CN117980143A/zh
Priority to JP2022557107A priority patent/JPWO2023047936A1/ja
Priority to KR1020237043591A priority patent/KR20240075775A/ko
Publication of WO2023047936A1 publication Critical patent/WO2023047936A1/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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2457/00—Electrical equipment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a biaxially oriented polyester film having surfaces with specific properties on both sides of the film.
  • Thermoplastic resins are used in various industrial fields because of their good workability. Products obtained by processing these thermoplastic resins into films play an important role in today's life, such as industrial applications, optical product applications, packaging applications, and magnetic recording tape applications. In recent years, electronic information equipment has become smaller, finer, and more highly integrated, and along with this, there is a demand for improved workability of process films used in the manufacturing process of electronic information equipment. As a process film for manufacturing electronic parts, there is an increasing demand for a process film for releasing green sheets, which is used in the manufacturing process of multilayer ceramic capacitors, which has been growing remarkably in recent years.
  • a green sheet is a thin film ceramic obtained by coating and drying a ceramic slurry on a release film, and the surface smoothness of the release film is important in the peeling process. This is because if the uneven shape of the release surface is transferred to the surface of the green sheet, defects resulting from the uneven shape will occur in the subsequent step of laminating the green sheets. However, the surface of the release layer may become rough due to the propagation of unevenness on the surface of the base film, and the surface shape of the opposite side of the release surface may be transferred to the release surface during roll winding. It is difficult to retain its surface smoothness. In particular, since the thickness of the green sheet for the next generation will be as thin as 0.5 ⁇ m, it is necessary to maintain the smoothness of the release surface before and after roll winding.
  • Patent Document 1 discloses a method of controlling the surface roughness of both surfaces by controlling the particle size contained in the film, thereby suppressing the uneven transfer to the green sheet.
  • Patent Document 1 has a high particle content and is insufficient for next-generation applications.
  • the green sheet laminated via the release resin coating layer is coated and peeled when the sheet is formed.
  • surface defects and sheet cracking caused by the transfer of uneven shapes to the green sheet can be greatly suppressed.
  • the present invention has the following configurations. i.e. [I] A biaxially oriented polyester film having a surface (side A) that satisfies the following (1) and a surface (side B) opposite to the side A that satisfies the following (2).
  • the A surface has protrusions, and among the values of the maximum protrusion height in each field of view obtained by the following method, the maximum protrusion height value corresponding to the top 5% value is Sp5%A (nm ), the Sp5%A should be 110 or less.
  • the B surface has protrusions, and the maximum protrusion height value corresponding to the top 5% of the maximum protrusion height values in each field of view obtained by the following method is Sp5%B (nm ), Sp5%B is 150 or more and 1000 or less.
  • Sp5%B nm
  • Sp5%B 150 or more and 1000 or less.
  • Maximum projection height measurement method Using 10 objective lenses with a scanning white light interference microscope (VertScan), surface images of 561 ⁇ m square field of view are measured for 100 fields, the maximum protrusion height Sp value in each field of view is obtained, and the value corresponding to the top 5% of them is Sp5% value.
  • N80nmA is 0.4 or less, where projections are present on the A surface and the number of projections with a height of 80 nm or more is N80nmA (pieces/ mm2 ). biaxially oriented polyester film.
  • N 10 nm A is 300 or more and 1000 or less [I] or [ II] biaxially oriented polyester film.
  • the biaxially oriented polyester film according to any one of [I] to [III], wherein the polyester resin layer (P1 layer) is the layer having the A side.
  • the thickness of the R1 layer is The biaxially oriented polyester film according to any one of [VII] to [IX], wherein T R1 ( ⁇ m) is from 0.01 to 1.00.
  • the layer having the B surface is the P2 layer
  • the structure of at least three layers having a P3 layer containing particles between the P1 layer and the P2 layer [I] to [X] A biaxially oriented polyester film according to any one of [XII]
  • T P2 /D P2 is 1 or more and 5 or less, where T P2 ( ⁇ m) is the thickness of the P2 layer and D P2 ( ⁇ m) is the maximum particle diameter of the particles contained in the P2 layer.
  • [XVI] The biaxially oriented polyester film according to any one of [I] to [XV], which is used as a support film for green sheet molding in the process of manufacturing a laminated ceramic capacitor.
  • the biaxially oriented polyester film of the present invention has highly smooth surfaces on both sides, and is excellent in process transportability (suppression of surface scratches and surface scraping) and roll windability (suppression of winding wrinkles and winding misalignment).
  • process transportability suppression of surface scratches and surface scraping
  • roll windability compression of winding wrinkles and winding misalignment.
  • by suppressing the rough transfer of the uneven shape of the film surface to the release layer after being wound as a roll not only the coatability and peelability of the laminated green sheet, but also the cracking of the green sheet and the surface Defects can be suppressed.
  • the biaxially oriented polyester film of the present invention has good surface smoothness and releasability, and is particularly useful as a support film for green sheet molding in the process of manufacturing laminated ceramic capacitors.
  • FIG. 2 is a conceptual diagram showing Sp5%A measured with a scanning white light interference microscope.
  • FIG. 2 is a conceptual diagram showing Sp5%B measured with a scanning white light interference microscope.
  • 3-layer configuration diagram of the biaxially oriented polyester film of the present invention Four-layer configuration diagram of a biaxially oriented polyester film having the coating layer of the present invention
  • the present invention relates to biaxially oriented polyester films.
  • the biaxially oriented polyester film of the present invention has a surface (A side) that satisfies the following (1), and a biaxially oriented polyester film that has a side (B side) opposite to the A side that satisfies the following (2): is.
  • a side a biaxially oriented polyester film that has a side (B side) opposite to the A side that satisfies the following (2): is.
  • Sp5%A (nm) is the maximum protrusion height value corresponding to the top 5% of the maximum protrusion heights in each field of view obtained by the following method.
  • A is 110 or less.
  • Sp5%B (nm) is the value of the maximum protrusion height corresponding to the top 5% of the maximum protrusion height in each field of view obtained by the following method
  • Sp5% B is 150 or more and 1000 or less.
  • Maximum projection height measurement method Using 10 objective lenses with a scanning white light interference microscope (VertScan), surface images of 561 ⁇ m square field of view are measured for 100 fields, the maximum protrusion height Sp value in each field of view is obtained, and the value corresponding to the top 5% of them is Sp5% value. A detailed measurement method will be described later.
  • the biaxially oriented polyester film of the present invention comprises a polyester resin layer (P1) having the A side, an intermediate layer (P3), and a layer (P2) having the opposite side (B side) to the A side, and the P1 layer It is preferable to take a three-layer lamination structure of /P3 layer/P2 layer. Further, the biaxially oriented polyester film of the present invention has a coating layer (R1) having the A side, a polyester resin layer (P1), an intermediate layer (P3), and a side opposite to the A side (B side) and preferably has a four-layer lamination structure of R1 layer/P1 layer/P3 layer/P2 layer.
  • the maximum projection height value Sp5%A (nm) corresponding to the top 5% of the maximum projection height in each field obtained by the method described later in the present invention is ISO 25178 by the software attached to the scanning white interference microscope. It is a value measured by a measurement method described later based on.
  • the Sp5%A (nm) on the A side is 110 or less, thereby reducing the number of surface defects in the green sheet, green sheet cracks, and the number of defects in the process of laminating the green sheets to produce a ceramic capacitor. can be done.
  • a more preferable range of the Sp5%A (nm) on the A surface is 100 or less, more preferably 80 or less.
  • the number of projections N 80nm A (number/mm 2 ) having a height of 80 nm or more on the A side is preferably 0.4 or less. It reflects the number of protrusions that transfer the formation of coarse irregularities to the surface of the green sheet.
  • the number of protrusions corresponding to each height in the present invention is a value measured by a measurement method described below based on ISO 25178 using software attached to a scanning white light interference microscope.
  • a more preferable range for the number of protrusions N80nmA (number/ mm2 ) having a height of 80 nm or more is 0.3 or less, more preferably 0.2 or less.
  • the number of protrusions N 10 nm A (number/mm 2 ) having a height of 10 nm or more on the A side is preferably 300 or more and 1000 or less. , is a value that reflects the slipperiness of the surface A with the process rolls.
  • a preferable range of the number of protrusions N 10 nm A (number/mm 2 ) having a height of 10 nm or more is 400 or more and 1000 or less.
  • the surface opposite to A surface (B surface) in the present invention has projections, and the maximum projection height value corresponding to the top 5% of the maximum projection height in each field of view obtained by the method described later is Sp5 %B (nm), Sp5%B is 150 or more and 1000 or less.
  • Sp5%B is required to be a release layer for a green sheet during roll winding or a laminated high smoothness. It is a value that reflects the height of the protrusions that transfer the uneven shape to the surface of the green sheet that is applied.
  • the Sp5%B (nm) in the present invention is a value determined by software attached to a scanning white light interference microscope and measured according to ISO 25178 by the measurement method described below.
  • the Sp5%B (nm) is 1000 or less, surface defects in green sheets, green sheet cracks, and defects in the process of laminating green sheets to produce a ceramic capacitor can be reduced.
  • a more preferable upper limit of the Sp5%B (nm) is 700 or less.
  • the biaxially oriented polyester film can have good lubricity on both sides of the film, and the occurrence of wrinkles during roll winding can be suppressed. can do.
  • a more preferable lower limit of the Sp5%B (nm) is 180 or more, more preferably 200 or more.
  • the biaxially oriented polyester film of the present invention has a layer (P1 layer) containing a polyester resin as a main component, and when the surface of the P1 layer is the outermost surface of the biaxially oriented polyester film, The surface is preferably the A surface.
  • the fact that the surface of the P1 layer is the outermost surface of the biaxially oriented polyester film and is the A side may be referred to as the A side of the P1 layer. Since the P1 layer surface is the outermost surface of the biaxially oriented polyester film and is the A side, when a coating layer is provided on the P1 layer surface, the maximum protrusion height and the number of protrusions on the coating layer surface are within a preferable range.
  • the P1 layer surface satisfies the requirements for the A surface, This is preferable because it facilitates control so that the surface of the coating layer satisfies the requirements of the A side.
  • the biaxially oriented polyester film referred to in the present invention indicates a film containing a polyester resin as a main component.
  • the term "main component” as used herein refers to a component contained in an amount exceeding 50% by mass in 100% by mass of the total components of the film.
  • the polyester resin referred to in the present invention is obtained by polycondensation of a dicarboxylic acid component and a diol component.
  • the term "constituent" refers to a minimum unit that can be obtained by hydrolyzing a polyester.
  • Dicarboxylic acid constituents constituting such polyesters include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,8-naphthalene.
  • Dicarboxylic acids, aromatic dicarboxylic acids such as 4,4′-diphenyldicarboxylic acid and 4,4′-diphenyletherdicarboxylic acid, and ester derivatives thereof can be mentioned.
  • Diol constituents constituting such polyesters include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. and alicyclic diols such as cyclohexanedimethanol and spiroglycol, and diols in which a plurality of the above diols are linked.
  • Polyester resins used in the present invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalenedicarboxylate (PEN), and dicarboxylic acid of PET from the viewpoint of mechanical properties and transparency.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene-2,6-naphthalenedicarboxylate
  • dicarboxylic acid of PET from the viewpoint of mechanical properties and transparency.
  • a copolymer obtained by copolymerizing isophthalic acid or naphthalene dicarboxylic acid as a part of the acid component, and a polyester obtained by copolymerizing cyclohexanedimethanol, spiroglycol, or diethylene glycol as a part of the diol component of PET are preferably used. is preferred.
  • the polyester film in the biaxially oriented polyester film of the present invention is preferably biaxially oriented.
  • the biaxial orientation improves the mechanical strength of the film, making it less prone to wrinkling and improving windability. can be uniform across the film.
  • the term "biaxially oriented" as used herein refers to a pattern showing a biaxially oriented pattern in wide-angle X-ray diffraction.
  • a polyester film can generally be obtained by stretching an unstretched thermoplastic resin sheet in the longitudinal direction and the width direction of the sheet, followed by heat treatment to complete crystal orientation. Details will be described later.
  • a method for adjusting the Sp5%A (nm) to the above range is to decompose and remove deteriorated foreign substances derived from the polyester resin present on the surface and remove coarse protrusions.
  • plasma surface treatment by atmospheric pressure glow discharge From the viewpoint of suppressing excessive deterioration of the polyester resin constituting the A side of the P1 layer due to the surface treatment and generation of foreign matters, it is more preferable to use plasma surface treatment by atmospheric pressure glow discharge.
  • Plasma surface treatment by atmospheric pressure glow discharge may be performed on the unstretched film after extrusion or on the stretched film in the polyester film manufacturing process. From the viewpoint of imparting properties, it is most preferable to subject the unstretched film to plasma surface treatment by atmospheric pressure glow discharge. This is because the amorphous polyester portion is scraped off by the plasma surface treatment by atmospheric pressure glow discharge, and the crystalline polyester portion remaining on the surface in the subsequent stretching process grows crystals as convex portions, forming fine protrusions on the surface. .
  • the atmospheric pressure here is in the range of 700 Torr to 780 Torr.
  • the film to be treated is guided between the facing electrodes and the earth roll, a plasma-exciting gas is introduced into the apparatus, and a high-frequency voltage is applied between the electrodes to excite the gas into plasma. Glow discharge is performed between electrodes. As a result, the film surface is finely processed (ashed) to form projections.
  • a plasma-excitable gas is a gas that can be plasma-excited under the conditions described above.
  • plasma-exciting gases include rare gases such as argon, helium, neon, krypton and xenon, nitrogen, carbon dioxide, oxygen, fluorocarbons such as tetrafluoromethane, and mixtures thereof.
  • one type of plasma-excitable gas may be used alone, or two or more types may be combined at an arbitrary mixing ratio. It preferably contains oxygen in addition to at least one of argon, oxygen, and carbon dioxide, from the viewpoint of increasing activity when excited by plasma.
  • a highly active plasma-exciting gas the number of fine protrusions formed on the film surface can be increased, and lubricity may be further improved.
  • the frequency of the high frequency voltage in plasma processing is preferably in the range of 1 kHz to 100 kHz.
  • the discharge treatment intensity (E value) obtained by the following method is preferably in the range of 50 to 2000 W min/m 2 from the viewpoint of forming protrusions, more preferably 150 to 1000 W min/m 2 . be.
  • E value Vp ⁇ Ip/(S ⁇ Wt)
  • E E value (W min/m 2 )
  • Vp applied voltage
  • Ip applied current
  • S processing speed (m/min)
  • Wt processing width (m)
  • T P1 ( ⁇ m) When the thickness of the P1 layer of the present invention is T P1 ( ⁇ m), T P1 ( ⁇ m) is preferably 2 or more and 10 or less.
  • T P1 ( ⁇ m) of the P1 layer By setting the thickness T P1 ( ⁇ m) of the P1 layer to 2 or more, even when coarse particles are added to the P3 layer and P4 layer described later, the shape of the particles has an effect on the A surface as much as possible. can do.
  • the particle diameter of the peak top indicating the maximum exceeds 800 nm, the A surface is affected.
  • the thickness T P1 ( ⁇ m) of the P1 layer is more preferably 3 or more, more preferably 5 or more. Further, by setting the thickness T P1 ( ⁇ m) of the P1 layer to 10 or less, it is possible to increase the ratio of the intermediate layer (P3) to which recycled raw materials are applied while suppressing the thickness of all the film layers. A more preferable upper limit of the thickness T P1 ( ⁇ m) of the P1 layer is 8 or less.
  • the P1 layer of the biaxially oriented polyester film of the present invention contains particles, a heat stabilizer, an oxidation stabilizer, an antistatic agent, an organic/inorganic lubricant, and a nucleus to the extent that the effects of the present invention are not impaired.
  • Additives such as agents, dyes, dispersants, coupling agents, and wavelength conversion materials may be added.
  • the P1 layer of the biaxially oriented polyester film of the present invention may contain particles for the purpose of controlling the Sp5%A (nm) on the A surface of the P1 layer, but the particles should not be contained. is the more preferred form.
  • the particles to be added are not particularly limited, and either inorganic particles or organic particles may be used, and two or more types of particles may be used together.
  • inorganic particles include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, alumina ( ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina), Mica, mica, titanium mica, zeolite, talc, clay, kaolin, lithium fluoride, calcium fluoride, montmorillonite, zirconia, wet silica, dry silica, colloidal silica, and the like.
  • the organic particles include organic particles and core-shell type organic particles having acrylic resins, styrene resins, silicone resins, polyimide resins, and the like as constituent components.
  • the average particle size of the particles is preferably 10 nm or more and 100 nm or less in order to prevent the formation of protrusions of 110 nm or more on the surface.
  • the adjacent P1 layer contains particles with a high Mohs hardness, and the average primary particle diameter of the particles is 50 nm or less, so that the P1 layer itself is in a dispersed state, thereby increasing the apparent hardness of the P1 layer itself and suppressing deformation. By doing so, scraping of the coating layer can be suppressed.
  • alumina Mohs hardness: 9
  • a more preferable range of the average primary particle size is 30 nm or less, and more preferably 20 nm or less.
  • the amount of particles added to the P1 layer is preferably 0.5% by mass or less.
  • the amount of particles to be added is 0.5% by mass or less.
  • a preferable range for the addition amount of alumina particles having an average primary particle size of 50 nm or less is 0.3% by mass or less.
  • T P1 /D P1 is 20 or more and 100 or less. It is preferable to be T P1 / D P1 is a value that reflects the occupancy ratio of particles in the P1 layer .
  • the amount of particles contained in the P1 layer of the present invention is not particularly limited, it is preferably 0.5% by mass or less in order to prevent the formation of protrusions of 110 nm or more on the surface. It is more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less.
  • the P2 layer preferably contains a polyester resin as a main component, like the P1 layer.
  • the particles contained in the P2 layer of the present invention preferably have an average particle diameter of 100 nm or more and 900 nm or less as determined by the method described later.
  • the average particle size of the particles is contained as the average particle size of the particles (which will be described in detail later in the description of the measurement method).
  • the contact area between films can be efficiently reduced and air entrainment during winding can be suppressed. may be possible.
  • the particle size is 30 nm or more and less than 1200 nm. It preferably has a peak, and more preferably has one or more peaks in the particle size range of 30 nm or more and less than 400 nm and in the particle size range of 400 nm or more and less than 1200 nm.
  • T P2 / D P2 is preferably 1 or more and 5 or less.
  • T P2 /D P2 is a value that reflects the occupancy ratio of particles in the P2 layer, and by setting T P2 /D P2 to 1 or more, it is possible to suppress the formation of coarse protrusions on the B surface, By setting T P2 /D P2 to 5 or less, the air can be easily released when the films are overlapped with each other, and the occurrence of wrinkles during roll winding can be suppressed.
  • T P2 which is the thickness of the P2 layer
  • T P2 is not particularly limited, by making it 1 or more and 10 or less, it is easy to control the relationship between the particles and the laminate thickness, and the P3 layer described later with the same film thickness. ratio can be increased to improve recyclability.
  • the particles contained in the P2 layer of the biaxially oriented polyester film of the present invention are not limited as in the P1 layer, and either inorganic particles or organic particles may be used.
  • inorganic particles include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, alumina ( ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina), Mica, mica, titanium mica, zeolite, talc, clay, kaolin, lithium fluoride, calcium fluoride, montmorillonite, zirconia, wet silica, dry silica, colloidal silica, and the like.
  • organic particles include organic particles and core-shell type organic particles having acrylic resins, styrene resins, silicone resins, polyimide resins, and the like as constituent components.
  • the amount of particles added to the P2 layer of the biaxially oriented polyester film of the present invention is not particularly limited, but from the viewpoint of controlling the Sp5%B (nm) on the B side within a preferable range, the content concentration in the P2 layer is It is preferable to make it 3 mass % or less. If the amount exceeds 3% by mass, the film may partially become cloudy even if particles having an average particle size within the preferred range are used, and the light transmittance and haze, which will be described later, may deviate from the preferred ranges. It is more preferably 2% by mass or less, still more preferably 1% by mass or less.
  • a method of extruding in a state of being laminated together with the P1 layer and the P3 layer described later (co-extrusion method) or extruding other resin layer raw materials into the film during film formation
  • co-extrusion method a method of extruding in a state of being laminated together with the P1 layer and the P3 layer described later
  • extruding other resin layer raw materials into the film during film formation It is possible to use a method in which the film is put into a machine, melt-extruded, and laminated while being extruded from a die (melt lamination method), or a method in which films after film formation are laminated via an adhesive layer.
  • the biaxially oriented polyester film of the present invention preferably has a P3 layer between said P1 and P2 layers. Particles and additives contained in the P3 layer can be added as long as they do not affect the smoothness of the surface of the P1 layer (side A) and the surface of the P2 layer (side B). Above all, it is preferable to utilize the biaxially oriented polyester film of the present invention as a recycled raw material and add it to the P3 layer from the viewpoint of reducing the environmental load as a film product.
  • the recycled raw material of the biaxially oriented polyester film is a recycled raw material composed of the entire biaxially oriented polyester film, but the P1 layer, especially the P1 layer laminated with the coating layer (R1 layer) described later, or the part from which the P2 layer is removed. It may be a recycled raw material consisting of As a method for producing recycled raw materials, generally used methods can be used, for example, a method of crushing scrap film generated in the slitting process in the film production process and then pressing and compacting it into flakes, or a method of crushing and then melting.
  • Examples include a method of pulverizing once and then compacting it into flakes, and a method of melting and extruding after crushing.
  • the content of recycled raw material components in the P3 layer should be 15% by mass or more and 50% by mass or less. is preferred. By setting the content of the recycled raw material to 15% by mass or more, it is possible to utilize the waste film generated in the film-forming process described above as a biaxially oriented polyester film without discarding it. , it is possible to suppress excessive deterioration in strength and durability as a biaxially stretched film.
  • the polyester film in the biaxially oriented polyester film of the present invention is preferably biaxially oriented.
  • the biaxial orientation improves the mechanical strength of the film, making it less prone to wrinkling and improving windability. can be uniform across the film.
  • the term "biaxially oriented" as used herein refers to a pattern showing a biaxially oriented pattern in wide-angle X-ray diffraction.
  • a polyester film can generally be obtained by stretching an unstretched thermoplastic resin sheet in the longitudinal direction and the width direction of the sheet, followed by heat treatment to complete crystal orientation. Details will be described later.
  • the intrinsic viscosity (IV) of the polyester film is preferably 0.50 dl/g or more, more preferably 0.60 dl/g or more.
  • IV is a number that reflects the length of the molecular chain, and the longer the molecular chain, the easier it is to clearly form a crystalline part and an amorphous part in the same molecular chain. This is preferable because it facilitates formation of finer protrusions.
  • the IV by setting the IV to 0.50 dl/g or more, it is possible to suppress the difficulty of film formation due to the progress of crystallization due to the short polyester molecular chain and frequent breakage in the stretching process.
  • the biaxially oriented polyester film of the present invention has the above-described P1 layer, P2 layer, and P3 layer, and has a structure of at least three layers (P1 layer/P3 layer/ P2 layer).
  • the method for laminating other resin layers such as the P1 layer, the P2 layer and the P3 layer is not particularly limited, but may be a co-extrusion method described later, or a method in which another resin layer raw material is put into an extruder during film formation.
  • a method of laminating while extruding and extruding from a die (melt lamination method), a method of laminating films after film formation with an adhesive layer interposed, etc. can be used.
  • a coextrusion method is preferably used.
  • the biaxially oriented polyester film of the present invention preferably has a static friction coefficient ( ⁇ s) of 0.3 or more and 0.8 or less on both sides of the film (the A side and the B side) from the viewpoint of film roll windability.
  • ⁇ s static friction coefficient
  • the static friction coefficient ( ⁇ s) on both sides of the film is set to 0.8 or less. By doing so, it is possible to suppress the occurrence of wrinkles due to the adhesion of both sides of the film during roll winding.
  • the upper limit of the coefficient of static friction ( ⁇ s) of both sides of the film is more preferably 0.7 or less, and even more preferably 0.6 or less.
  • the biaxially oriented polyester film of the present invention may be provided with a coating layer (R1 layer), which will be described later, on the outermost surface.
  • R1 layer a coating layer
  • the configuration is composed of the above-mentioned P1 layer, P2 layer, P3 layer and the coating layer R1 layer, and the R1 layer and the P2 layer are the outermost layers. It is preferable to have a configuration of at least four layers (R1 layer/P1 layer/P3 layer/P2 layer) arranged in a row.
  • T When the total layer thickness of the biaxially oriented polyester film of the present invention is T ( ⁇ m), T is preferably 15 or more and 100 or less.
  • T is preferably 15 or more and 100 or less.
  • T ( ⁇ m) By setting the total layer thickness T ( ⁇ m) to 15 or more, film breakage occurs due to stretching and heat treatment during the processing process when used as a film for the manufacturing process of a biaxially oriented polyester film and a laminated ceramic capacitor manufacturing process.
  • T ( ⁇ m) By setting the total layer thickness T ( ⁇ m) to 100 or less, the film rigidity of the biaxially oriented polyester film is prevented from increasing excessively, and the processability in the heat lamination process in the manufacture of electronic parts is improved.
  • a more preferable range of the total layer thickness T ( ⁇ m) is 20 or more and 50 or less.
  • ⁇ T is preferably 5.0 or less.
  • the thickness unevenness ⁇ T (%) is obtained by measuring the film thickness in the width direction of the film roll by the measurement method described later, T AVE ( ⁇ m) is the average film thickness, T MAX ( ⁇ m) is the maximum value of the film thickness, It is a value represented by the following formula (1) when the minimum value is T MIN ( ⁇ m).
  • ⁇ T (%) 100 ⁇ (T MAX - T MIN )/T AVE Equation (1)
  • ⁇ T (%) within a preferable range for example, in order to reduce unevenness in the thickness of the polyester film, a method of making the slit width of the T die uniform in the width direction during extrusion, or a tenter described later.
  • the temperature applied to the biaxially oriented polyester film is made uniform in the width direction by reducing the width direction unevenness of the stretching temperature and adjusting the relaxation treatment to an appropriate range, thereby reducing thickness unevenness due to poor stretching.
  • a method for suppressing the occurrence can be mentioned.
  • the thickness unevenness can be reduced by performing the plasma surface treatment by the above-described atmospheric pressure glow discharge.
  • the aforementioned plasma surface treatment by atmospheric pressure glow discharge can also be used as a technique for reducing unevenness in the thickness of a coating layer (R1 layer) when the coating layer is provided.
  • the functional groups generated by the surface treatment remain on the surface of the P1 layer even after the formation of the polyester film, thereby improving the affinity with the coating layer and improving the coatability and the partial thickness of the coating layer. This is because the occurrence of unevenness is suppressed. These effects are particularly likely to be obtained when T R1 ( ⁇ m), which is the thickness of the coating layer, is 0.01 or more and 0.30 or less.
  • the biaxially oriented polyester film of the present invention may have a coating layer (R1) having the A side on the outermost surface.
  • the R1 layer is a release agent (A) and a coating composition containing at least one resin or compound (B) selected from epoxy resins, melamine resins, oxazoline compounds, carbodiimide compounds, acrylic resins, and silicone resins. It is preferable to be configured using
  • the R1 layer preferably contains at least one of an acrylic resin and a silicone resin as a main component.
  • CaR (°) which is the water contact angle of the R1 layer surface
  • CaR (°) which is the water contact angle of the R1 layer surface
  • a more preferable lower limit of CaR (°) is 105 or more.
  • the amount of silicone compound contained in the P1 layer the details of the measurement method will be described later. It can be calculated by the ratio (P/K) [ ⁇ ] of the peak intensity (P) of the fragment derived from polydimethylsiloxane to K).
  • the tape peeling force from the surface (A side) of the R1 layer obtained by the measurement method described later is FA ( mN/19 mm), FA is preferably 5 or more and 50 or less.
  • FA mN/19 mm
  • the green sheet made of thin film ceramic such as barium titanate can be peeled off without damage or defects, and FA (mN/19 mm) is set to 5 or more. In this way, it is possible to prevent the green sheet from being unintentionally lifted from the surface during process transportation.
  • a more preferable range of the surface tape peeling force FA (mN/19 mm) is 5 or more and 30 or less.
  • the release agent (A) as used in the present invention means a compound that imparts release properties to the surface of the coating layer by being contained in the coating composition.
  • Examples of the release agent (A) that can be used in the present invention include long-chain alkyl group-containing resins, olefin resins, fluorine compounds, and wax compounds. Among them, long-chain alkyl group-containing resins are preferable because they can impart good releasability.
  • long-chain alkyl group-containing compounds may be used. Specifically, long-chain alkyl-based compounds "Ashioresin” (registered trademark) series manufactured by Asio Sangyo Co., Ltd., Lion Specialty Chemicals “Pyroyl” series of long-chain alkyl compounds manufactured by Co., Ltd., and "Resem” series of aqueous dispersions of long-chain alkyl compounds manufactured by Chukyo Yushi Co., Ltd. can be used.
  • the releasing agent (A) preferably has an alkyl group with 12 or more carbon atoms, and more preferably has an alkyl group with 16 or more carbon atoms.
  • the hydrophobicity is increased, and sufficient release performance as the release agent (A) can be exhibited. If the number of carbon atoms in the alkyl group is less than 12, the release performance may be insufficient.
  • the upper limit of the carbon number of the alkyl group is not particularly limited, it is preferably 25 or less because production is easy.
  • the resin having an alkyl group having 12 or more carbon atoms is more preferably a resin having a side chain of an alkyl group having 12 or more carbon atoms on a polymethylene main chain. Since the main chain is polymethylene, the number of hydrophilic groups in the entire resin is reduced, so that the release effect of the release agent (A) can be further enhanced.
  • the alkyl group having 12 carbon atoms corresponds to the alkyl group among the signals obtained from the laminated film, for example, by TOF-SIMS (TOF-SIMS: time-of-flight secondary ion mass spectrometry). It can be evaluated using the strength of the object. At this time, it is possible to perform continuous measurement in the depth direction by using a cutting method based on the ion sputtering method in combination, and it is also possible to evaluate the distribution state of the alkyl group-containing compound.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • resins melamine resins and acrylic resins are preferable because the interaction between hydroxyl groups is easily controlled and the resin layer is easily changed by high-temperature heating.
  • epoxy resins examples include sorbitol polyglycidyl ether-based cross-linking agents, polyglycerol polyglycidyl ether-based cross-linking agents, diglycerol polyglycidyl ether-based cross-linking agents, and polyethylene glycol diglycidyl ether-based cross-linking agents.
  • a cross-linking agent or the like can be used.
  • the epoxy resin a commercially available one may be used. -521, EX-421, EX-313, EX-810, EX-830, EX-850, etc.), diepoxy-polyepoxy compounds manufactured by Sakamoto Pharmaceutical Co., Ltd. (SR-EG, SR-8EG, SR-GLG etc.), an epoxy cross-linking agent "EPICLON" (registered trademark) EM-85-75W manufactured by Dainippon Ink Mfg. .
  • the melamine resin that can be used as the resin or compound (B) includes, for example, melamine, methylolated melamine derivatives obtained by condensing melamine and formaldehyde, and partially or completely ethers obtained by reacting methylolated melamine with a lower alcohol. compounds, mixtures thereof, and the like can be used.
  • the melamine resin may be either a condensate of a monomer or a polymer of dimers or higher, or a mixture thereof.
  • Methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used as lower alcohols used for etherification.
  • one having an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule can be used as an imino group-type methylated melamine resin, a methylol group-type melamine resin, or a methylol group-type melamine resin.
  • an imino group-type methylated melamine resin a methylol group-type melamine resin
  • a methylol group-type melamine resin or a methylol group-type melamine resin.
  • a methylolated melamine resin is most preferably used.
  • the oxazoline compound that can be used as the resin or compound (B) has an oxazoline group as a functional group in the compound, contains at least one monomer containing an oxazoline group, and has at least one It is preferably composed of an oxazoline group-containing copolymer obtained by copolymerizing other monomers.
  • Monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be used, and a mixture of one or more of these can also be used.
  • 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
  • At least one other monomer used for the oxazoline group-containing monomer is a monomer copolymerizable with the oxazoline group-containing monomer, such as methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid esters such as 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methacrylic acid esters, acrylic acid, methacrylic acid, itaconic acid, malein Unsaturated carboxylic acids such as acids, unsaturated nitriles such as acrylonitrile and methacrylonitrile, unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide and N-methylolmethacrylamide, vinyl acetate and vinyl propionate Vinyl esters, vinyl ethers such as methyl vinyl ether and e
  • the carbodiimide compound that can be used as the resin or compound (B) is a compound having one or more carbodiimide groups or cyanamide groups in a tautomeric relationship thereof as functional groups in the molecule.
  • Specific examples of such carbodiimide compounds include dicyclohexylmethanecarbodiimide, dicyclohexylcarbodiimide, tetramethylxylylenecarbodiimide, urea-modified carbodiimide, and the like, and these can be used singly or in combination of two or more. .
  • the coating layer of the biaxially oriented polyester film of the present invention may contain an isocyanate compound as the resin or compound (B).
  • Isocyanate compounds include, for example, tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanatohexane, and an adduct of tolylene diisocyanate and hexanetriol.
  • an adduct of tolylene diisocyanate and trimethylolpropane polyol-modified diphenylmethane-4,4′-diisocyanate, carbodiimide-modified diphenylmethane-4,4′-diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3′-bitrylene -4,4'diisocyanate, 3,3'dimethyldiphenylmethane-4,4'-diisocyanate, metaphenylene diisocyanate and the like.
  • a blocked isocyanate-based compound in which the isocyanate group is masked with a blocking agent or the like can be preferably used in terms of the pot life of the coating material.
  • heat is applied in the drying process after applying the coating composition to the polyester film, so that the blocking agent is dissociated and the isocyanate groups are exposed, resulting in the progress of the cross-linking reaction.
  • the acrylic resin that can be used as the resin or compound (B) is not particularly limited, but is preferably composed of alkyl methacrylate and/or alkyl acrylate.
  • Alkyl methacrylates and/or alkyl acrylates include methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, and 2-hydroxy methacrylate.
  • the urethane resin that can be used as the resin or compound (B) is a resin obtained by reacting a polyhydroxy compound and a polyisocyanate compound by a known urethane resin polymerization method such as emulsion polymerization or suspension polymerization. is preferred.
  • polyhydroxy compounds include polyethylene glycol, polypropylene glycol, polyethylene/propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaptolactone, polyhexa
  • polyhydroxy compounds include polyethylene glycol, polypropylene glycol, polyethylene/propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaptolactone, polyhexa
  • examples include methylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, polycarbonate diol, glycerin and the like.
  • polyisocyanate compounds examples include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, adducts of tolylene diisocyanate and trimethylenepropane, and adducts of hexamethylene diisocyanate and trimethylolethane.
  • the silicone resin that can be used as the resin or compound (B) may be a type containing a curable silicone resin as a main component, or a type containing a modified silicone resin as a main component. Any curing reaction type such as addition type, condensation type, ultraviolet curing type, electron beam curing type, non-solvent type, heat and ultraviolet curing combination type, etc. can be used as the type of curable silicone resin.
  • Modified silicone resins may be modified silicone resins obtained by graft polymerization with organic resins such as epoxy resins, urethane resins and alkyl resins.
  • the mass ratio of the release agent (A) and the resin or compound (B) is preferably in the range of 10/90 to 45/55. It is more preferably in the range of 15/85 to 45/55. Within this range, the release agent (A) in the resin layer becomes a sufficient amount, and the initial tape peeling force can be improved. At the same time, the amount of the resin or compound (B), which is easily changed by heating, is also sufficient, so that the release property before and after heating can be improved.
  • the coating layer (R1) of the present invention may contain particles within a range that does not affect the Sp5%A (nm) of the A side.
  • T R1 When the thickness of the R1 layer in the present invention is T R1 ( ⁇ m), T R1 is preferably 0.01 or more and 1.00 or less. By setting the T R1 ( ⁇ m) to 0.01 or more, it is possible to exhibit a peeling function against the mating member, and by setting it to 1.00 or less, uneven drying of the coating composition is reduced, and local application It is possible to suppress the occurrence of uneven formation of layers.
  • a more preferable range of the thickness TR1 of the R1 layer is 0.01 or more and 0.30 or less.
  • the method of forming the R1 layer in the present invention is not particularly limited, but when the coating composition is used, an off-coating method in which coating is performed after the polyester film is manufactured, or coating and drying are performed during the polyester film manufacturing process. Either of the in-line coating techniques performed can be used.
  • oxides of metals such as titanium, aluminum, barium, lead, zirconium, silicon, yttrium, barium titanate, Pb(Mg 1/3 , Nb 2/3 )O 3 , Pb(Sm 1/2 , Nb 1/2 )O 3 , Pb(Zn 1/3 , Nb 2/3 )O 3 , PbThO 3 , PbZrO 3 and the like can be used. These may be used singly or in combination of two or more.
  • Polymers such as polyurethane resin, urea resin, melamine resin, epoxy resin, vinyl acetate resin, acrylic resin, polyvinyl alcohol, and polyvinyl butyral can be used as the binder resin that constitutes the ceramic slurry. These may be used singly or in combination of two or more.
  • the solvent for the ceramic slurry may be either water or an organic solvent.
  • organic solvents toluene, ethanol, methyl ethyl ketone, isopropyl alcohol, ⁇ -butyl lactone and the like can be used. These may be used singly or in combination of two or more.
  • a plasticizer, a dispersant, an antistatic agent, a surfactant, and the like may be added to the ceramic slurry, if necessary.
  • a conventional polymerization method can be adopted.
  • a dicarboxylic acid component such as terephthalic acid or an ester-forming derivative thereof and a diol component such as ethylene glycol or an ester-forming derivative thereof are transesterified or esterified by a known method, followed by a melt polymerization reaction. You can get it by doing.
  • the polyester obtained by the melt polymerization reaction may be subjected to a solid phase polymerization reaction at a temperature not higher than the melting point temperature of the polyester.
  • the polyester film of the present invention can be obtained by a conventionally known production method. Specifically, the polyester film of the present invention uses a method (melt casting method) in which a dried raw material is heated and melted in an extruder as necessary, and extruded from a nozzle onto a cooled cast drum to be processed into a sheet. be able to. As another method, the raw material is dissolved in a solvent, the solution is extruded from a die onto a support such as a cast drum or an endless belt to form a film, and then the solvent is removed from the film layer by drying to form a sheet. A method (solution casting method) or the like can also be used.
  • an extruder is used for each layer constituting the biaxially oriented polyester film, the raw materials for each layer are melted, and these are placed between the extruder and the die.
  • a method co-extrusion method
  • An unstretched film is produced by statically contacting the laminated sheet on a cast drum cooled to a surface temperature of 20° C. or higher and 60° C. or lower and solidifying by cooling.
  • the surface temperature of the cast drum By setting the surface temperature of the cast drum to 20°C or higher, the crystalline polyester portion on the surface of the unstretched film can be further increased, and the effect of forming fine projections after stretching by plasma surface treatment by atmospheric pressure glow discharge can be obtained. can be done. Further, by setting the surface temperature of the cast drum to 60° C. or less, the adhesion of the unstretched film to the cast drum can be suppressed, and an unstretched film with little thickness unevenness in the film running direction can be obtained. A more preferable range of the surface temperature of the cast drum is 25°C or higher and 55°C or lower.
  • the unstretched film obtained here is subjected to surface treatment such as plasma surface treatment by atmospheric pressure glow discharge.
  • surface treatment such as plasma surface treatment by atmospheric pressure glow discharge.
  • These surface treatments may be performed immediately after obtaining an unstretched film or after stretching in the running direction of the film (hereinafter sometimes referred to as the longitudinal direction). It is preferable from the viewpoint of promoting the formation of protrusions.
  • the surface to be surface-treated may be either the surface in contact with the cast drum (drum surface) or the surface not in contact with the cast drum (non-drum surface).
  • the stretching conditions for biaxially stretching an unstretched film are not particularly limited. It is preferable that the film is guided to a group of rolls heated to the above, stretched in the longitudinal direction (longitudinal direction, that is, the traveling direction of the film), and cooled by a group of rolls set to a temperature of 20°C or higher and 50°C or lower.
  • the lower limit of the temperature of the heating rolls in longitudinal stretching is not particularly limited as long as the stretchability of the sheet is not impaired, but it is preferably higher than the glass transition temperature of the polyester resin used.
  • the preferred range of the draw ratio in the longitudinal direction is 3 times or more and 5 times or less. A more preferable range is 3 times or more and 4 times or less.
  • both ends of the film are held with clips and guided to a tenter, and in an atmosphere heated to a temperature of 70 ° C or higher and 160 ° C or lower, the film is stretched perpendicular to the longitudinal direction. It is preferable to stretch the film by 3 times or more and 5 times or less in the direction (width direction), and then heat-treat the stretched film to stabilize the internal orientation structure.
  • the thermal history temperature of the film during the heat treatment it should be confirmed by the minute endothermic peak (sometimes referred to as Tmeta) temperature appearing directly below the melting point temperature measured by a differential scanning calorimeter (DSC) described later.
  • the set temperature of the tenter device is preferably set so that the maximum temperature in the tenter is 200 ° C. or higher and 250 ° C. or lower.
  • the melting point of the resin it is preferable to set the melting point of the resin to ⁇ 55° C. or less and ⁇ 5° C. or less.
  • Tmeta which represents the thermal history temperature of the film during heat treatment
  • the range of Tmeta is preferably 190°C or higher and 245°C or lower for the reasons described above when the polyester resin is the main component.
  • a more preferable range is 210° C. or higher and 240° C. or lower.
  • relaxation treatment may be performed in the range of 1% or more and 6% or less.
  • relaxation treatment may be performed in the range of 1% or more and 6% or less.
  • the draw ratio is 3 times or more and 5 times or less in each of the longitudinal direction and the width direction. It is more preferable to be 20 times or less.
  • the area ratio is 9 times or more, the molecular orientation of the biaxially oriented polyester film obtained can be promoted and the durability can be improved, and when the area ratio is 22 times or less, tearing during stretching is suppressed. be able to.
  • drying is performed at 60° C. or higher and 110° C. or lower to form a coating layer.
  • the drying time is not particularly limited, but by setting it to 30 seconds or less, the productivity of the coating process can be improved.
  • a known coating method can be used, for example, a roll coating method such as gravure coating or reverse gravure coating, a bar coating method using a wire bar, a die coating method, a lip coating method, and a spray coating method.
  • a coating method, an air knife coating method, and the like can be mentioned.
  • the Y-axis of the sample film is measured in any one direction, then rotated 120 degrees, and then measured 120 degrees. Measurements are taken in the rotated direction, and the average of the respective measurement results is taken as the number of projections of the sample.
  • the sample film to be measured is sandwiched between two metal frames with rubber packing, and the sample surface is measured with the film in the frame in a stretched state (a state in which slack and curl are removed from the sample).
  • the obtained microscopic image was subjected to image processing under the following conditions using the surface analysis software VS-Viewer Version 10.0.3.0 built into the microscope, and the arithmetic mean surface roughness and each height Find the number of protrusions of
  • Image processing is performed in the following order. ⁇ Interpolation processing: Complete interpolation ⁇ Filter processing: Median (3 x 3 pixels) ⁇ Surface correction: 4th order.
  • Top 5% value of maximum protrusion height (Sp5%A and Sp5%B) 100 fields of view are measured using a scanning white interference microscope on the surface (A surface) of the biaxially oriented polyester film, and each measurement image subjected to the image processing described above is displayed in the "parameter sheet” window in the surface analysis software.
  • Projection analysis processing is performed under the following conditions. ⁇ Analysis type: Rush analysis ⁇ Image correction: None ⁇ Processing Height threshold: 0.08 ⁇ m (0.01 ⁇ m during N 10 nm A analysis described later) Particle shaping: None Reference height: Zero plane (average plane) ⁇ Determination target height/depth: -10000 ⁇ m ⁇ h ⁇ 10000 ⁇ m Maximum diameter: -10000 ⁇ m ⁇ d ⁇ 10000 ⁇ m Volume: V ⁇ 0.0000 ⁇ m 3 Aspect ratio: r ⁇ 0.0000 ⁇ Histogram: Number of divisions 50 The same operation is performed in all of the 100 fields of view measured, and the average value is defined as the number of projections N 80 nm A (pieces/mm 2 ) having a height of 80 nm or more on the A side of the sample.
  • the measurement image (561 ⁇ m ⁇ 561 ⁇ m) obtained by performing the microscope image observation by the above-mentioned method and performing the above-mentioned image processing is automatically calculated by the following formula: Use the plane of the average value (Ave) of the heights found in .
  • lx range length in the X direction in each measurement image subjected to the above image processing ly: range length in the Y direction in each measurement image subjected to the image processing described above
  • the surface analysis software VS-Viewer Version 10.0.3.0 incorporated in the microscope was used to perform the following Particle analysis processing is performed under the conditions, and the number of particles displayed on the "particle analysis" screen detected at a height threshold of 10 nm (R 10 nm , height threshold setting value: 0.01 ⁇ m) is measured.
  • the number of protrusions with a height of 10 nm or more is obtained.
  • the same operation is performed in all 100 fields of view that were measured, and the average value is defined as the number of projections N 10 nm A (pieces/mm 2 ) having a height of 10 nm or more on the A side of the sample.
  • lamination thickness (ii) lamination thickness (T P1 , T P2 )
  • a cross section of a biaxially oriented polyester film is cut with a microtome in a direction parallel to the width direction of the film.
  • the cross section is observed with a scanning electron microscope at a magnification of 5,000 to 20,000 times to determine the thickness ratio of each laminated layer.
  • the thickness of each layer is calculated from the obtained lamination ratio and the thickness of all the layers obtained in the above item (i).
  • Thickness (T R1 ) of coating layer (R1) Biaxially oriented polyester films are dyed with ruthenium tetroxide ( RuO4 ) and/or osmium tetroxide ( OsO4 ). A biaxially oriented polyester film is frozen and cut in the thickness direction of the film to obtain 10 ultra-thin slice samples (10 pieces) for cross-sectional observation of the resin layer. A cross section of each sample is observed with a TEM (transmission electron microscope: H7100FA type manufactured by Hitachi, Ltd.) at a magnification of 10,000 to 1,000,000 to obtain a photograph of the cross section. The measured values of the thickness of the release resin coating layer (R1 layer) having the surface at 10 points (10 pieces) are averaged to obtain the thickness T R1 ( ⁇ m) of the release resin coating layer.
  • RuO4 ruthenium tetroxide
  • OsO4 osmium tetroxide
  • Width direction thickness unevenness ⁇ T of the film roll A continuous contact thickness gauge (KG601B manufactured by Anritsu Co., Ltd.) is used to measure the full width of the film roll of the biaxially oriented polyester film in the width direction. In the obtained film thickness, the thickness unevenness obtained by subtracting the minimum value (T MIN ) from the maximum value (T MAX ) according to the following formula (1) is divided by the average value (T AVE ) and converted into percent units. Obtain ⁇ T (%). The measurement is performed three times every 15 m in the film unwinding direction, ⁇ T is obtained for each measurement, and the maximum value thereof is defined as the thickness unevenness ⁇ T (%) of the biaxially oriented polyester film.
  • the width direction of the film roll refers to a direction perpendicular to the film unwinding direction within the film plane of the biaxially oriented polyester film of the present invention.
  • the thickness unevenness is measured in two directions: a specific direction and a direction tilted 90° in the film plane from the measurement direction. and let the maximum value thereof be the thickness unevenness ⁇ T (%) of the biaxially oriented polyester film.
  • the thickness unevenness in the width direction at the trisecting point of the full width in the unwinding direction Measurements are performed, and the maximum value thereof is taken as the thickness unevenness ⁇ T (%) of the biaxially oriented polyester film.
  • tape peel force was measured as follows. First, an acrylic polyester adhesive tape (manufactured by Nitto Denko Corporation, Nitto 31B tape, 19 mm width) is pasted on the coating layer of the biaxially oriented polyester film of the present invention, and a 2 kgf roller is reciprocated once from above, Create a tape laminated laminated film. After that, the tape-laminated laminated film was allowed to stand in an environment of 25° C. and 65% RH for 24 hours, and then, using a universal testing machine “Autograph AG-1S” manufactured by Shimadzu Corporation, a peel angle of 180° and a tensile test were performed. The peel force (N/19 mm) is measured at a speed of 300 mm/min.
  • E. Static friction coefficient ( ⁇ s) After conditioning the humidity of the biaxially oriented polyester film of the present invention at 23° C. and 65% RH, two strips with a width of 75 mm and a length of 100 mm were cut out so that the direction of the film production line was the longitudinal direction, and the sample was obtained.
  • a slip coefficient measuring device (model ST-200, manufactured by Techno Needs Co., Ltd.) is used to measure under an atmosphere of 23° C. and 65% RH.
  • a strip-shaped sample is set and fixed on the measuring sample stand of the apparatus so that the direction of pulling the strip sample becomes the longitudinal direction of the strip sample and the surface side faces upward.
  • ⁇ sp/C [ ⁇ ]+K[ ⁇ ] 2 ⁇ C (2)
  • ⁇ sp (solution viscosity/solvent viscosity) - 1
  • K is the Huggins constant (assumed to be 0.343).)
  • (1-1) Dissolve a measurement sample in 100 mL of ortho-chlorophenol to prepare a solution with a concentration higher than 1.2 g/100 mL.
  • the weight of the measurement sample subjected to ortho-chlorophenol is defined as the weight of the measurement sample.
  • Terminal carboxyl group content (unit: eq/t, indicated as COOH content in the table) It was measured by the method of Maulice. (Reference MJ Maulice, F. Huizinga, Anal. Chem. Acta, 22, 363 (1960)). That is, 0.5 g of a measurement sample (polyester (raw material) or polyester film from which only the P1 layer is separated) is weighed with an accuracy within 0.001 g. 50 ml of a solvent obtained by mixing o-cresol/chloroform at a mass ratio of 7/3 is added to the sample, heated to an internal temperature of 90° C., and then heated and stirred for 20 minutes to dissolve the sample. Also, the mixed solvent alone is similarly heated separately as a blank solution.
  • Terminal carboxyl group amount (equivalent/t) ⁇ (V1-V0) x N x f ⁇ x 1000/S
  • V1 is the titrant volume (mL) in the sample solution
  • V0 is the titrant volume (mL) in the blank solution
  • N is the titrant normality (N)
  • f is the titrant factor
  • S is the polyester composition. It is the mass (g) of the object.
  • Cross-sectional photographs were selected from different arbitrary measurement fields, and the circle-equivalent diameters of 400 or more particles arbitrarily selected from the cross-sectional photographs were measured to obtain the volume-based average particle diameter.
  • the equivalent circle diameters of 200 or more particles are measured for each particle, and the average particle diameter is obtained from the average value of the volume-based equivalent circle diameters. .
  • volume-based particle size distribution analysis was performed on the particle diameters obtained by the method described in (i) above.
  • the particle diameters on the horizontal axis in the volume-based particle size distribution are expressed in classes at intervals of 10 nm with 0 nm as the starting point. From the particle size distribution chart of the obtained particles, the particle size of the peak top indicating the maximum was read.
  • A Among the 10 rolls, 1 or more and 2 or less rolls with surface scratches.
  • B Out of 10 rolls, 3 or more and 4 or less rolls had surface scratches.
  • C Out of 10 rolls, 5 or more and 6 or less rolls with surface scratches.
  • D Out of 10 rolls, 7 or more rolls had surface scratches.
  • a to C are good as surface defects during process transportation, and AA is the most excellent among them.
  • the surface abrasion resistance during process transportation is evaluated by the following test using a tape running tester and a single blade, and evaluated from the amount of scraped powder adhering to the single blade.
  • a biaxially oriented polyester film having a coating layer was cut into a tape shape having a width of 12.65 mm and a length of 25 cm.
  • a tape running tester SFT-700 type manufactured by Yokohama System Laboratory Co., Ltd.
  • a load of 300 g is applied to the end of the tape-shaped sample in an atmosphere of 23 ° C. and 65% RH, and the length direction 10 cm at a running speed of 3.33 cm/sec under tension.
  • the sample is run while a carbon steel razor blade described below is pressed against the surface of the release resin coating layer (said surface) of the biaxially oriented polyester film having the coating layer by 1 mm.
  • the side of the single-edged blade through which the film has passed is observed with an optical microscope at a magnification of 200 to determine the height of the shavings deposited on the cutting edge.
  • the piled-up height of the shavings was observed at any five points in the range of 12.65 mm where the single-edged film passed through, and the average value thereof was evaluated as the surface shaving resistance of the sample during process transportation.
  • A: The accumulated height of scraped powder is 20 ⁇ m or less.
  • B The piled-up height of scraped powder is more than 20 ⁇ m and 30 ⁇ m or less.
  • C Accumulation height of scraped powder is more than 30 ⁇ m and 40 ⁇ m or less.
  • D The accumulated height of shaving powder exceeds 40 ⁇ m.
  • a to C are good in terms of surface scraping property during process transportation, and A is the best among them.
  • the biaxially oriented polyester film of the present invention is formed at a film forming speed of 100 m/min or more, and 10 consecutive rolls of 5000 m are taken. The 10 film rolls thus obtained were evaluated for occurrence of winding misalignment as follows.
  • winding misalignment A to C are good, and A is the best among them.
  • process transportability A to C are good, and A is the best among them.
  • the biaxially oriented polyester film of the present invention is formed at a film forming speed of 100 m/min or more, and 10 consecutive rolls of 5000 m are taken. The occurrence of winding wrinkles on the ten film rolls thus obtained was evaluated as follows.
  • A Among 10 rolls, 2 or less rolls have winding wrinkles.
  • B Out of 10 rolls, 3 or more and 4 or less rolls had winding wrinkles.
  • C 5 or more and 6 or less rolls with winding wrinkles among 10 rolls.
  • D Among 10 rolls, 7 or more rolls had winding wrinkles.
  • a to C are good for winding wrinkles, and A is the best among them.
  • A Repelling occurred 0 times out of 10 times.
  • B Repelling occurs 1 time or more and 3 times or less out of 10 times.
  • C Repelling occurs 4 times or more and 5 times or less out of 10 times.
  • D Repelling occurs 6 times or more out of 10 times.
  • a to C are good, and among them, A is the best.
  • peel force of green sheet is 5 mN/19 mm or more and 20 mN/19 mm or less
  • a to C are good, and among them, A is the best.
  • AA No surface defects with a circle-equivalent average diameter of 0.5 ⁇ m or more are observed on all three sheets
  • B One out of three sheets
  • a to C are good as the surface defects after peeling of the green sheet having surface defects of 0 ⁇ m or more, and AA is the most excellent among them.
  • PET-1 To dimethyl terephthalate (DMT), 1.9 mol of ethylene glycol and magnesium acetate tetrahydrate per 100 parts by weight of DMT were added, and phosphoric acid was added. 0.015 parts by weight was added to carry out heat transesterification. Subsequently, 0.025 parts by weight of antimony trioxide was added, and the mixture was heated and polycondensed under vacuum to obtain polyester pellets containing substantially no particles. The obtained melt-polymerized PET had a glass transition temperature of 81° C., a melting point of 255° C., and an intrinsic viscosity of 0.55.
  • the obtained polyester pellets were dried at 160°C for 6 hours to crystallize, and then solid-phase polymerization was performed at 220°C under a vacuum of 0.3 Torr for 8 hours to obtain solid-phase polymerized PET.
  • the resulting solid phase polymerized PET had a glass transition temperature of 81° C., a melting point of 255° C., and an intrinsic viscosity of 0.63.
  • PET-2 the biaxially oriented polyester film was formed in the same manner as in Example 1 with a configuration in which only PET-1 was used as the constituent resin of the intermediate layer (P3 layer).
  • PET-2 which is a recycled raw material, was obtained by extruding.
  • the obtained recycled material PET-2 had a glass transition temperature of 81° C., a melting point of 255° C., and an intrinsic viscosity of 0.60.
  • the constituent resin of the intermediate layer (P3 layer) is only PET-1, and the constituent resin of the P2 layer is Silica-6, which will be described later, so that it is 1.0% with respect to the entire P2 layer.
  • a biaxially oriented polyester film having a coating layer was obtained by forming a film in the same manner as in Example 1 except that a coating layer was provided by in-line coating using coating composition C described later. After forming and peeling a green sheet on the coating layer surface (above A side) of the biaxially oriented polyester film having the obtained coating layer, according to the above-mentioned "Evaluation of green sheet coating and peelability" method, biaxially The coating layer of the oriented polyester film was removed with an alkaline solution, and only the remaining biaxially oriented polyester film was pulverized, remelted at 280° C. and extruded to obtain PET-3 as a recycled raw material. The obtained recycled material PET-3 had a glass transition temperature of 81° C., a melting point of 255° C., and an intrinsic viscosity of 0.59.
  • long-chain alkyl group-containing resin long-chain alkyl group-containing resin (a-2) which is a block copolymer having an alkyl group with 22 carbon atoms.
  • the obtained long-chain alkyl group-containing resin (a-1) was emulsified as follows to obtain a water-based resin emulsion. 375 g of water was placed in a 1 L homomixer, 45 g of polyoxyethylene nonylphenyl ether, 30 g of polyoxyethylene polyoxypropylene glycol, 200 g of long-chain alkyl group-containing resin a1, and 150 g of toluene were sequentially added and heated to 70°C. and stirred evenly. This mixed solution was transferred to a pressurized homogenizer for emulsification, and the pressure was further reduced while heating to distill off the toluene. • Polyether-modified polydimethylsiloxane Momentive's polyether-modified polydimethylsiloxane (TSF4446; solid concentration 100%) was used.
  • b-2 A coating agent containing a silicone component manufactured by Shin-Etsu Silicone Co., Ltd., model number KR-400 was used.
  • ⁇ Acrylic resin (b-3) Methyl methacrylate ( ⁇ ), hydroxyethyl methacrylate ( ⁇ ), urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., Artresin (registered trademark) UN-3320HA, the number of acryloyl groups is 6) ( ⁇ ) are charged at a mass ratio of ( ⁇ )/( ⁇ )/( ⁇ ) 94/1/5, and sodium dodecylbenzenesulfonate is added as an emulsifier by 2 masses per 100 mass parts in total of ( ⁇ ) to ( ⁇ ). were added and stirred to prepare a mixed liquid 1.
  • a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was prepared.
  • a reaction apparatus was charged with 60 parts by weight of the mixed solution 1, 200 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate as a polymerization initiator, and heated to 60° C. to prepare a mixed solution 2.
  • Mixed solution 2 was held for 20 minutes while being heated at 60°C.
  • mixed solution 3 was prepared from 40 parts by weight of mixed solution 1, 50 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate. Subsequently, using a dropping funnel, the mixed liquid 3 was dropped into the mixed liquid 2 over 2 hours to prepare a mixed liquid 4.
  • the mixed solution 4 was held for 2 hours while being heated to 60°C. After cooling the obtained mixed liquid 4 to 50° C. or lower, it was transferred to a container equipped with a stirrer and a pressure reducing device. 60 parts by weight of 25% aqueous ammonia and 900 parts by weight of pure water are added thereto, and the isopropyl alcohol and unreacted monomers are recovered under reduced pressure while heating to 60° C., and the acrylic resin (b -3) was obtained.
  • ⁇ Methylolated melamine resin (b-4) Sanwa Chemical Co., Ltd., "Nikalac” (registered trademark) MW-035 (solid concentration: 70% by mass, solvent: water) was used.
  • PET-1, PET-2, MB-B, and MB-C were dried under reduced pressure at 180°C for 2.5 hours, and then blended so that the amounts of the P1 layer, P2 layer, and P3 layer shown in Table 3 were obtained. Then, it is supplied to each of the three extruders, melt-extruded, filtered with a filter, and then joined in a feed block so as to be laminated into three layers (P1 layer / P3 layer / P2 layer structure), and then a T die.
  • An unstretched film was obtained by winding the film on a cooling cast roll maintained at 42° C. via an electrostatic casting method and cooling and solidifying.
  • This unstretched film is guided between the opposing electrodes and the earth roll, nitrogen gas is introduced into the device, and the atmospheric pressure glow discharge is applied to the surface of the P1 layer under the condition that the treatment intensity (E value) is 250 W min / m 2 .
  • Plasma treatment was performed by
  • the unstretched film after the treatment is passed through a static elimination roll whose roll temperature is set to 30°C, it is successively biaxially stretched under the conditions shown in Table 4.
  • the film was stretched 4.4 times, heat-treated at 235° C. under a constant length, and subjected to 3% relaxation treatment in the width direction to obtain a biaxially oriented polyester film having a thickness of 35 ⁇ m.
  • the structure of the obtained biaxially oriented polyester film, analysis of particles contained in the film, surface properties, and film properties were as shown in Tables 5 and 6.
  • the surface properties of the surface of the P1 layer containing polyester resin as the main component were as follows. Top 5% value of maximum protrusion height: 75 nm Number of protrusions with a height of 80 nm or more: 0.1/mm 2 Number of protrusions with a height of 10 nm or more: 500/mm 2
  • the coating composition A was applied by gravure coating so as to be as shown in Table 7, and dried at a drying temperature of 100°C for 30 seconds.
  • a coating layer (R1) having a final thickness of 0.1 ⁇ m was formed to obtain a biaxially oriented polyester film.
  • the structure of the biaxially oriented polyester film is a four-layer structure of R1 layer/P1 layer/P3 layer/P2 layer.
  • the thickness unevenness of the obtained biaxially oriented polyester film having the coating layer was as shown in Table 7.
  • the production suitability and application suitability evaluation are as follows. Repellency), peelability, sheet cracking, and surface defects).
  • Example 2 In Example 2, except that the particles were contained in the P1 layer so as to have the concentration shown in Table 3, and in Examples 3 and 4, the particles contained in the P2 layer were changed so as to be as shown in Table 3.
  • a biaxially oriented polyester film having a thickness of 35 ⁇ m was obtained in the same manner as in Example 1.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing the polyester resin as the main component in Examples 2 to 4 were as follows.
  • Example 2 Top 5% value of maximum protrusion height: 110 nm Number of protrusions with a height of 80 nm or more: 0.3/mm 2 Number of protrusions with a height of 10 nm or more: 700/mm 2 (Examples 3 and 4) Top 5% value of maximum protrusion height: 75 nm Number of protrusions with a height of 80 nm or more: 0.1/mm 2 Number of protrusions with a height of 10 nm or more: 500/mm 2 Production suitability and application suitability evaluation are shown in Table 8. Although it deteriorated, both were within the range of practical use. As for other properties, the film was good as in Example 1.
  • Example 3 the winding misalignment and the surface defects of the green sheet were worse than in Example 1, but both were within the range of practical use.
  • the film was good as in Example 1.
  • Example 4 winding wrinkles were worse than in Example 1, but both were within the range of practical use.
  • the film was good as in Example 1.
  • Example 5 and 6 a 35 ⁇ m-thick biaxially oriented polyester film and a biaxially oriented polyester film were obtained in the same manner as in Example 1, except that the thickness of the P1 layer was changed as shown in Table 4.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7.
  • the surface properties of the surface of the P1 layer containing the polyester resin as the main component in Examples 5 and 6 were as follows.
  • Example 5 Top 5% value of maximum protrusion height: 90 nm Number of protrusions with a height of 80 nm or more: 0.4/mm 2 Number of protrusions with a height of 10 nm or more: 600/mm 2 (Example 6) Top 5% value of maximum protrusion height: 95 nm Number of protrusions with a height of 80 nm or more: 0.5/mm 2 Number of protrusions with a height of 10 nm or more: 650 / mm 2 Production suitability and application suitability evaluation are shown in Table 8. Cracking was further aggravated, and surface defects were also aggravated compared to Example 1, but both were within the range of practical use. As for other properties, the film was good as in Example 1.
  • Example 7 to 9 a biaxially oriented polyester film with a thickness of 35 ⁇ m was obtained in the same manner as in Example 1, except that the treatment intensity of plasma treatment by atmospheric pressure glow discharge was changed as shown in Table 4.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing polyester resin as a main component in Examples 7 to 9 were as follows.
  • Example 7 Top 5% value of maximum protrusion height: 75 nm Number of protrusions with a height of 80 nm or more: 0.06/mm 2 Number of protrusions with a height of 10 nm or more: 400/mm 2 (Example 8) Top 5% value of maximum protrusion height: 75 nm Number of protrusions with a height of 80 nm or more: 0.1/mm 2 Number of protrusions with a height of 10 nm or more: 330/mm 2 (Example 9) Top 5% value of maximum protrusion height: 75 nm Number of protrusions with a height of 80 nm or more: 0.1/mm 2 Number of protrusions with a height of 10 nm or more: 300/mm 2
  • Table 8 The production suitability and application suitability evaluations are shown in Table 8. In Example 7, surface scratches were worse, and in addition to surface scratches, winding misalignment and green sheet surface defects were worse in Examples 8 and 9 than in Example 1. However, both
  • Example 10-12 In Examples 10 and 11, except that the coating composition applied on the biaxially oriented polyester film was changed as shown in Table 7, and in Example 12, the thickness of the coating layer was changed as shown in Table 7. obtained a biaxially oriented polyester film having a thickness of 35 ⁇ m in the same manner as in Example 1.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing the polyester resin as the main component in Examples 10 to 12 were as follows.
  • Example 10-12 Top 5% value of maximum protrusion height: 75 nm Number of protrusions with a height of 80 nm or more: 0.1/mm 2 Number of protrusions with a height of 10 nm or more: 500/mm 2 Evaluations of suitability for production and suitability for use are shown in Table 8. In Example 10, green sheet coatability was improved, and in Examples 11 and 12, green sheet peelability was improved compared to Example 1. As for other properties, the film was good as in Example 1.
  • Example 13 a biaxially oriented polyester film with a thickness of 35 ⁇ m was obtained in the same manner as in Example 1, except that the structure of the biaxially oriented polyester film was changed as shown in Tables 3 and 4 to provide a two-layer structure. .
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing polyester resin as a main component in Example 13 were as follows.
  • Example 13 Top 5% value of maximum protrusion height: 110 nm Number of protrusions with a height of 80 nm or more: 0.4/mm 2 Number of protrusions with a height of 10 nm or more: 600/mm 2
  • Table 8 The production suitability and application suitability evaluations are shown in Table 8.
  • surface scraping, green sheet cracking, and surface defects were worse than in Example 1, but both were within the range of practical use.
  • the film was good as in Example 1.
  • Example 14 a biaxially oriented polyester film having a thickness of 35 ⁇ m was obtained in the same manner as in Example 1, except that the structure of the biaxially oriented polyester film was changed as shown in Tables 3 and 4.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing polyester resin as a main component in Example 14 were as follows.
  • Example 14 surface abrasion and green sheet cracking were worse than in Example 1, but both were within the range of practical use. As for other properties, the film was good as in Example 1.
  • Example 15 and 16 In Examples 15 and 16, the configuration of the biaxially oriented polyester film was changed as described in Tables 3 and 4 in addition to applying PET-3, which is a recycled raw material, to the P3 layer, which is an intermediate layer.
  • PET-3 which is a recycled raw material
  • a 35 ⁇ m-thick biaxially oriented polyester film having a three-layer laminate structure was obtained in the same manner as in Example 1.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing the polyester resin as the main component in Examples 15 and 16 were as follows.
  • Example 15 Top 5% value of maximum protrusion height: 100 nm Number of protrusions with a height of 80 nm or more: 0.4/mm 2 Number of protrusions with a height of 10 nm or more: 700/mm 2
  • Example 16 Top 5% value of maximum protrusion height: 85 nm Number of protrusions with a height of 80 nm or more: 0.3/mm 2 Number of protrusions with a height of 10 nm or more: 600/mm 2
  • Table 8 The production suitability and application suitability evaluations are shown in Table 8.
  • Example 15 in the volume-based particle size distribution analysis of the intermediate layer, the particle size of the peak top showing the maximum peak exceeds 800 nm.
  • Example 16 by increasing the P1 layer thickness compared to Example 15, the surface defects improved while the sheet cracks worsened compared to Example 1, but eventually was also within the practical range. As for other properties, the film was good as in Example 1.
  • Example 17 a biaxially oriented polyester film having a thickness of 35 ⁇ m was obtained in the same manner as in Example 1, except that the structure of the biaxially oriented polyester film was changed as shown in Tables 3 and 4.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing polyester resin as a main component in Example 17 were as follows.
  • Example 17 had worse winding wrinkles than Example 1, but was within the range of practical use. As for other properties, the film was good as in Example 1.
  • Example 18 In Example 18, the structure of the biaxially oriented polyester film was as shown in Table 7, except that the coating composition constituting the coating layer and the thickness of the coating layer were changed in the same manner as in Example 1. An oriented polyester film was obtained. The structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing polyester resin as a main component in Example 18 were as follows.
  • Example 18 surface abrasion and releasability of the green sheet were worse than in Example 1, but both were within the range of practical use. As for other properties, the film was good as in Example 1.
  • Comparative example 1 a biaxially oriented polyester film with a thickness of 35 ⁇ m was obtained in the same manner as in Example 1, except that the particles contained in the P1 layer were changed as shown in Table 3.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7.
  • the surface properties of the surface of the P1 layer containing polyester resin as a main component in Comparative Example 1 were as follows. Top 5% value of maximum protrusion height: 130 nm Number of protrusions with a height of 80 nm or more: 0.5/mm 2 Number of protrusions with a height of 10 nm or more: 600/mm 2
  • the production suitability and application suitability evaluations are shown in Table 8. Comparative Example 1 was significantly inferior to Example 1 in sheet cracking and surface defects of the green sheet.
  • Comparative Example 4 a biaxially oriented polyester film with a thickness of 35 ⁇ m was obtained in the same manner as in Example 1, except that the particles contained in the P1 layer were changed as shown in Table 3.
  • the structure of the obtained biaxially oriented polyester film, particle content analysis, surface properties, and film properties were as shown in Tables 5-7. Further, the surface properties of the surface of the P1 layer containing polyester resin as a main component in Comparative Example 4 were as follows.
  • the biaxially oriented polyester film of the present invention has a release coated surface with excellent smoothness and a back surface with excellent smoothness. Since it is excellent in releasability and does not lose its smoothness even when a recycled raw material is used for the intermediate layer, it can be suitably used as a process film for green sheet release with less environmental load.

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Abstract

La présente invention vise à fournir un film de polyester à orientation biaxiale qui possède des surfaces hautement lisses sur les deux côtés, ce qui supprime la rugosité de transfert d'une forme de surface qui est transférée sur une couche de décollement après avoir été enroulé selon un rouleau, et ayant une surface de décollement lisse. À cet effet, l'invention concerne un film de polyester à orientation biaxiale dans lequel, parmi des valeurs de hauteurs maximales de saillie dans chaque champ de vision obtenu par le procédé suivant sur une surface (surface A) et l'autre surface (surface B), lorsque les valeurs des hauteurs maximales de saillie correspondant à des valeurs des 5 % les plus hautes sont respectivement définies comme étant Sp5%A (nm) et Sp5%B (nm), Sp5%A vaut 110 ou moins, et Sp5%B vaut de 150 à 1000. (Procédé de mesure de hauteur maximale de saillie) Dix objectifs sont utilisés avec un microscope à interférence de lumière blanche de type à balayage (VertScan) pour mesurer 100 champs de vision d'une image de surface dans un champ de vision à 561 µm, la valeur de hauteur maximale de saillie Sp dans chaque champ de vision est obtenue, et des valeurs correspondant aux 5 % les plus hautes sont définies comme étant les valeurs de Sp5%.
PCT/JP2022/033366 2021-09-24 2022-09-06 Film de polyester à orientation biaxiale WO2023047936A1 (fr)

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KR1020237043591A KR20240075775A (ko) 2021-09-24 2022-09-06 2축 배향 폴리에스테르 필름

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JP2010017932A (ja) * 2008-07-10 2010-01-28 Toyobo Co Ltd 離型フィルム
JP2019116086A (ja) * 2017-12-27 2019-07-18 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP2021024175A (ja) * 2019-08-02 2021-02-22 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP2021088185A (ja) * 2019-11-27 2021-06-10 東レ株式会社 二軸配向積層ポリエステルフィルムおよびその製造方法

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JP2015208939A (ja) 2014-04-28 2015-11-24 三菱樹脂株式会社 積層ポリエステルフィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010017932A (ja) * 2008-07-10 2010-01-28 Toyobo Co Ltd 離型フィルム
JP2019116086A (ja) * 2017-12-27 2019-07-18 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP2021024175A (ja) * 2019-08-02 2021-02-22 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP2021088185A (ja) * 2019-11-27 2021-06-10 東レ株式会社 二軸配向積層ポリエステルフィルムおよびその製造方法

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