WO2023190265A1 - Film de polyester biorienté - Google Patents

Film de polyester biorienté Download PDF

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Publication number
WO2023190265A1
WO2023190265A1 PCT/JP2023/012045 JP2023012045W WO2023190265A1 WO 2023190265 A1 WO2023190265 A1 WO 2023190265A1 JP 2023012045 W JP2023012045 W JP 2023012045W WO 2023190265 A1 WO2023190265 A1 WO 2023190265A1
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Prior art keywords
height
film
less
biaxially oriented
measurement
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PCT/JP2023/012045
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English (en)
Japanese (ja)
Inventor
幸平 佐藤
敏弘 千代
卓司 東大路
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東レ株式会社
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Publication of WO2023190265A1 publication Critical patent/WO2023190265A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to a biaxially oriented polyester film having at least one surface provided with a surface having specific properties.
  • polyester resin Due to its good processability, polyester resin is used in various industrial fields. Furthermore, products processed into film from these polyester resins (polyester films) play an important role in today's life, such as in industrial applications, optical product applications, packaging applications, and magnetic recording tape applications.
  • next-generation products will require very precise processing with a wiring width of 2 to 5 ⁇ m, and if particles are contained on the ultraviolet light irradiated surface (non-resist coated surface) of the support film, the ultraviolet light caused by the particles will be The resist shape may become non-uniform due to the scattering of the resist. For this reason, the ultraviolet light irradiated surface (non-resist-coated surface) of the support film is required to have smoother surface than ever before in addition to smoothness against the process metal roll. In addition to smoothing the resist-uncoated surface, it is also important to ensure smoothness between the resist-coated surface and the resist-uncoated surface in order to ensure film winding properties.
  • a polyester film is formed into a film in a manufacturing process and then wound into a roll shape. At this time, if the film surface is too smooth, the films will adhere to each other, resulting in poor film winding properties. Therefore, there is a known method of roughening the film surface to a certain extent (forming protrusions on the film surface) by adding particles to the film to ensure film windability (for example, Patent Document 1 ⁇ 4).
  • Patent Document 2 discloses a method of coating and laminating a particle-containing layer on the surface of a film.
  • coating layer components may fall off, and there is a concern that the falling coating layer components may affect the formation of a fine wiring resist.
  • Patent Document 3 discloses a method for forming fine protrusions that does not depend on particles by subjecting the film surface on the resist-coated side to plasma surface treatment using atmospheric pressure glow discharge.
  • nano-sized protrusions formed by this method are used in the winding process of the film with a structure in which the non-resist coated side is smoothed, and in the metal roll during transportation.
  • a high tension is applied to the film in a state of contact, there is a concern that the protrusions on the film surface will adhere to the film surface or the metal roll and be crushed, resulting in a decrease in slipperiness.
  • Patent Document 4 discloses a method that uses particles in combination with plasma surface treatment using atmospheric pressure glow discharge. Reinforcement of the surface protrusions by the particles is effective in improving the winding properties of the film in the film forming process, the slipperiness with metal rolls, and suppressing wrinkles and misalignment during winding.
  • smoothness better than that of the metal roll used in the film forming process and slipperiness against small-diameter rolls are required. Therefore, there is still a trade-off relationship between the slipperiness against the metal roll in the dry film resist process and the uniformity of the fine wiring resist shape, and it is difficult to achieve both.
  • an object of the present invention is to provide a biaxially oriented polyester film that is capable of achieving both a smooth resist-uncoated surface, slipperiness against a metal roll, and uniformity of the fine wiring resist shape.
  • the present invention has the following configuration. That is, [1] A biaxially oriented polyester film in which at least one surface is a surface A that satisfies (1a) and (2a) below when observed with AFM in a 5 ⁇ m square field under condition I below.
  • the number of valley regions with a height of -2 nm or less from the reference plane is 100 pieces/5 ⁇ m or more, and 500 pieces/5 ⁇ m or less
  • the average cross-sectional area of the valley areas with a height of -2 nm or less from the reference plane is 2000nm 2 or more, 8000nm 2 or less
  • ⁇ Measurement field of view 5 ⁇ m square ⁇ Sample line: 512 ⁇ Peak Force SetPoint: 0.0195V to 0.0205V ⁇ Feedback Gain: 10-20 ⁇ LP Deflection BW: 40kHz ⁇ ScanAsyst Noise Threshold: 0.5nm ⁇ Sample preparation: 23°C, 65%RH, left standing for 24 hours ⁇ AFM measurement environment: 23°C, 65%RH ⁇ Measurement sample preparation method: Paste double-sided tape on one side of an AFM sample disk (diameter 15 mm), and then attach the AFM sample disk and the surface of a biaxially oriented polyester film cut out to approximately 15 mm x 13 mm (longitudinal direction x width direction).
  • Measurement surface and the opposite side are pasted together to form a measurement sample.
  • ⁇ Number of measurements for measurement samples Change the location so that each measurement sample is separated by at least 5 ⁇ m, and perform measurements 20 times.
  • ⁇ Measurement value Analyze the images of the 20 measured locations, measure each numerical value, and treat the average value as each numerical value of the measurement sample.
  • ⁇ Calculation of valley area> The film surface image obtained under the conditions described in ⁇ AFM measurement method> is analyzed using the attached analysis software (NanoScope Analysis Version 1.40). Flatten processing is performed on the obtained height sensor image of the film surface.
  • the reference plane is a plane with a height of 0 nm determined under the Flatten processing conditions described below.
  • the Mean values of Total Count and Area which are calculated by setting the items on the Detect tab in the Particle Analysis analysis mode as shown below, are the number of valley regions less than -2 nm from the height reference plane and the average cross-sectional area, respectively.
  • ⁇ Flatten processing> ⁇ Flatten Order: 3rd ⁇ Flatten Z Thresholding Direction: No theresholding ⁇ Find Threshold for: the whole image ⁇ Flatten Z Threshold %: 0.00% ⁇ Mark Excluded Data: Yes ⁇ Particle Analysis mode setting> (Detect tab) ⁇ Threshold Height: -2.00nm ⁇ Feature Direction: Below ⁇ X Axis: Absolute ⁇ Number Histogram Bins: 512 ⁇ Histogram Filter Cutoff: 0.00 nm ⁇ Min Peak to Peak: 1.00 nm ⁇ Left Peak Cutoff: 0.00000% ⁇ Right Peak Cutoff: 0.00000% (Modify tab) ⁇ Boughbirhood
  • O1s-A/O1s-a>1.000, C1s+O1s+N1s 100
  • the thickness removed by argon etching is confirmed by measuring the thickness before and after argon etching through cross-sectional observation using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the etched surface a is subjected to measurement of each element type under the same conditions as the XPS measurement conditions described above.
  • ESCA 5800 manufactured by ULVAC-PHI
  • Data processing conditions> Using the analysis software "MultiPak", the concentration of each element is determined from the ratio of the integral values of the XPS spectra of C1s, O1s, and N1s obtained by narrow measurement.
  • the surface A' is a surface A that satisfies the following (1a) and (2a) when observed with AFM in a 5 ⁇ m square field of view under the following condition I. , the biaxially oriented polyester film according to [2].
  • the number of valley regions with a height of -2 nm or less from the reference plane is 100 pieces/5 ⁇ m or more, and 500 pieces/5 ⁇ m or less
  • the average cross-sectional area of the valley areas with a height of -2 nm or less from the reference plane is 2000 nm 2 or more, 8000 nm 2 or less
  • Condition I Same conditions as Condition I described in [1].
  • [4] The biaxially oriented polyester film according to [1] or [3], which satisfies the following (1b) and (2b) when the surface A is observed by AFM with a 5 ⁇ m square field of view under the condition I.
  • the number of valley regions with a height of -2 nm or less from the reference plane is 150 pieces/5 ⁇ m ⁇ or more, and 450 pieces/5 ⁇ m ⁇ or less
  • the average cross-sectional area of the valley regions with a height of -2 nm or less from the reference plane is 4000 nm 2 or more, 6500 nm 2 or less [5]
  • the number of mountain regions with a height of +3 nm or more from the reference surface is 50
  • the number of mountain areas is calculated by the following method. ⁇ Calculation of number of mountain areas>
  • the film surface image obtained under the conditions described in ⁇ AFM measurement method> is analyzed using the attached analysis software (NanoScope Analysis Version 1.40). Flatten processing is performed on the obtained height sensor image of the film surface.
  • the reference plane is a plane with a height of 0 nm determined under the Flatten processing conditions described below.
  • the Total Count which is calculated by setting the items on the Detect tab in the Particle Analysis analysis mode as shown below, is the number of mountain regions with a height of +3 nm or more from the reference plane.
  • ⁇ Particle Analysis mode setting> (Detect tab) ⁇ Threshold Height: 3.00nm ⁇ Feature Direction: Above ⁇ X Axis: Absolute ⁇ Number Histogram Bins: 512 ⁇ Histogram Filter Cutoff: 0.00 nm ⁇ Min Peak to Peak: 1.00 nm ⁇ Left Peak Cutoff: 0.00000% ⁇ Right Peak Cutoff: 0.00000% (Modify tab) ⁇ Boughbirhood Size:3 ⁇ Number Pixels Off: 1 ⁇ Do not perform any Dilate/Erode operations.
  • ⁇ Calculation of average cross-sectional area of mountain area> The film surface image obtained under the conditions described in ⁇ AFM measurement method> is analyzed using the attached analysis software (NanoScope Analysis Version 1.40). Flatten processing is performed on the obtained height sensor image of the film surface.
  • the reference plane is a plane with a height of 0 nm determined under the Flatten processing conditions described below.
  • the Mean value of Area which is calculated by setting the items on the Detect tab in the Particle Analysis analysis mode as shown below, is the average cross-sectional area of the mountain region with a height of +3 nm or more from the reference plane.
  • ⁇ Particle Analysis mode setting> (Detect tab) ⁇ Threshold Height: 3.00nm ⁇ Feature Direction: Above ⁇ X Axis: Absolute ⁇ Number Histogram Bins: 512 ⁇ Histogram Filter Cutoff: 0.00 nm ⁇ Min Peak to Peak: 1.00nm ⁇ Left Peak Cutoff: 0.00000% ⁇ Right Peak Cutoff: 0.00000% (Modify tab) ⁇ Boughbirhood Size:3 ⁇ Number Pixels Off: 1 ⁇ Do not perform any Dilate/Erode operations.
  • Kurtosis is 2.0 or more and 10.0 or less when the surface A is observed with AFM in a 5 ⁇ m square field of view under the above ⁇ AFM measurement method> under the above condition I [1], [3] The biaxially oriented polyester film according to any one of [6]. The kurtosis is determined by the following method.
  • Arithmetic mean height is 0.5 nm or more and 2.0 nm or less
  • Maximum protrusion height is 20 nm or more and 150 nm or less
  • Condition III ⁇ Scanning white interference microscopy measurement method> A 6 cm x 6 cm sample was taken from the biaxially oriented polyester film, and each sample was examined using a scanning white interference microscope (equipment: "VertScan” (registered trademark) VS1540 manufactured by Hitachi High-Tech Science Co., Ltd.). Surface B is measured using a 50x objective lens, the measurement mode is set to WAVE mode, and 90 visual fields are measured with a measurement area of 113 ⁇ m ⁇ 113 ⁇ m.
  • the sample set is measured by setting the sample on a stage so that the measurement Y-axis is in the longitudinal direction of the sample film (the direction in which the film is wound).
  • measure so that the measurement Y-axis is in one arbitrary direction of the sample film, then measure so that it is in the direction rotated 120 degrees, and then again 120 degrees.
  • the sample is measured in the rotated direction, and the average of the measurement results is taken as the characteristic of that sample.
  • the sample film to be measured is sandwiched between two metal frames containing rubber gaskets, and the sample surface is measured with the film in the frame stretched (sagging and curling removed).
  • the obtained microscopic image is subjected to image processing under the following conditions using surface analysis software VS-Viewer Version 10.0.3.0 built into the microscope.
  • Image processing conditions Image processing is performed in the following order.
  • ⁇ Interpolation processing Complete interpolation
  • ⁇ Filter processing Median (3 x 3 pixels)
  • ⁇ Surface correction 4th order
  • the surface A was measured using the scanning white interference microscopy method, and for each measurement image that was processed under the image processing conditions, the ISO parameter analysis within the surface analysis software was performed with the following analysis conditions: "Parameters" and output the obtained numerical value group to the parameter sheet field.
  • Sa is the arithmetic mean height
  • Sp is the maximum protrusion height
  • 80 fields of view are obtained by excluding the upper and lower 5 fields from the value of each field of view.
  • the average values at are the arithmetic mean height and maximum protrusion height of the surface B, respectively.
  • ISO parameter analysis processing is performed under the following conditions.
  • NP1 is the number of coarse particles with a major diameter of 2.0 ⁇ m or more when observing 30 fields of view of an area of 1 ⁇ m in the thickness direction x 220 ⁇ m in the longitudinal direction x 290 ⁇ m in the width direction from the surface B using a laser microscope, then NP1 is 20 or less, the biaxially oriented polyester film according to any one of [1] to [10].
  • the film dimensional change rate when increasing the film temperature from 90°C to 130°C is ⁇ L90-130°C (ppm/°C)
  • the width direction (TD direction) and longitudinal direction (MD direction) The biaxially oriented polyester film according to any one of [1] to [11], wherein at least one direction is -50 or more and 150 or less.
  • the biaxially oriented polyester film according to any one of [1] to [12] which is used as a film for a dry film resist support.
  • the biaxially oriented polyester film according to any one of [1] to [12] which is used as a support film for green sheet molding in the process of manufacturing a multilayer ceramic capacitor.
  • the biaxially oriented polyester film of the present invention has at least one surface having specific properties, so it has excellent smoothness and slipperiness, and also has excellent toughness, and has a resist-uncoated surface. With a structure in which the film is smoothed, it is possible to achieve both film winding properties, smoothness on a metal roll, and uniformity of the fine wiring resist shape.
  • biaxially oriented polyester films of the first embodiment and the second embodiment are included in biaxially oriented polyester films.
  • the biaxially oriented polyester film of the first embodiment and the biaxially oriented polyester film of the second embodiment may be collectively referred to as the biaxially oriented polyester film of the present invention.
  • the "biaxially oriented polyester film” in the present invention refers to a film containing polyester resin as a main component.
  • the main component here refers to a component that is contained in an amount exceeding 50% by mass in 100% by mass of all components of the film.
  • the polyester resin referred to in the present invention is obtained by polycondensing a dicarboxylic acid component and a diol component.
  • a constituent component shows the minimum unit which can be obtained by hydrolyzing polyester.
  • dicarboxylic acid constituents constituting the polyester include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,8-naphthalenedicarboxylic acid.
  • -Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, and 4,4'-diphenyl ether dicarboxylic acid, or ester derivatives thereof.
  • examples of the diol constituents constituting the polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3- Examples include aliphatic diols such as butanediol, alicyclic diols such as cyclohexanedimethanol and spiroglycol, and those in which a plurality of the above-mentioned diols are connected.
  • polyester resins used in the present invention include, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalene dicarboxylate (PEN), and PET.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene-2,6-naphthalene dicarboxylate
  • PET PET
  • polyesters in which isophthalic acid or naphthalene dicarboxylic acid is copolymerized as part of the dicarboxylic acid component of PET and polyesters in which cyclohexanedimethanol, spiroglycol, and diethylene glycol are copolymerized as part of the diol component of PET.
  • polyethylene terephthalate is particularly preferred.
  • polyester film in the biaxially oriented polyester film of the present invention is biaxially oriented, the mechanical strength of the film is improved, wrinkles are less likely to form, and winding properties can be improved. Furthermore, by applying uniform stretching stress during the stretching process, the surface smoothness can be made uniform throughout the film.
  • polyester orientation refers to one that exhibits a biaxial orientation pattern in wide-angle X-ray diffraction.
  • a polyester film can generally be obtained by stretching an unstretched thermoplastic resin sheet in the longitudinal and width directions of the sheet, and then subjecting it to heat treatment to complete crystal orientation. Detailed film forming conditions will be described later.
  • One surface of the biaxially oriented polyester film of the first embodiment is a surface A that satisfies the following (1a) and (2a) when observed with an AFM in a 5 ⁇ m square field of view under the following condition I.
  • (1a) The number of valley regions with a height of -2 nm or less from the reference plane is 100 pieces/5 ⁇ m or more, and 500 pieces/5 ⁇ m or less
  • (2a) The average cross-sectional area of the valley areas with a height of -2 nm or less from the reference plane is 2000nm 2 or more, 8000nm 2 or less
  • Condition I ⁇ AFM measurement method> ⁇ Device: Bruker Atomic Force Microscope (AFM) Dimention Icon with ScanAsyst ⁇ Cantilever: Silicon nitride probe ScanAsyst Air ⁇ Scanning mode: ScanAsyst ⁇ Scanning speed: 0.977Hz - Scanning direction: Scanning is performed in the width direction
  • ⁇ Measurement field of view 5 ⁇ m square ⁇ Sample line: 512 ⁇ Peak Force SetPoint: 0.0195V to 0.0205V ⁇ Feedback Gain: 10-20 ⁇ LP Deflection BW: 40kHz ⁇ ScanAsyst Noise Threshold: 0.5nm ⁇ Sample preparation: 23°C, 65%RH, left standing for 24 hours ⁇ AFM measurement environment: 23°C, 65%RH ⁇ Measurement sample preparation method: Paste double-sided tape on one side of an AFM sample disk (diameter 15 mm), and cut out the AFM sample disk and the biaxially oriented polyester film of the present invention into a size of approximately 15 mm x 13 mm (longitudinal direction x width direction).
  • the surface opposite to the surface is pasted together to form a measurement sample.
  • ⁇ Number of measurements for measurement samples Change the location so that each measurement sample is separated by at least 5 ⁇ m, and perform measurements 20 times.
  • ⁇ Measurement value Analyze the images of the 20 measured locations, measure each numerical value, and treat the average value as each numerical value of the measurement sample.
  • ⁇ Calculation of valley area> The film surface image obtained under the conditions described in ⁇ AFM measurement method> is analyzed using the attached analysis software (NanoScope Analysis Version 1.40). Flatten processing is performed on the obtained height sensor image of the film surface.
  • the reference plane is a plane with a height of 0 nm determined under the Flatten processing conditions described below.
  • the Mean values of Total Count and Area which are calculated by setting the items on the Detect tab in the Particle Analysis analysis mode as shown below, are the number of valley regions less than -2 nm from the height reference plane and the average cross-sectional area, respectively.
  • ⁇ Flatten processing> ⁇ Flatten Order: 3rd ⁇ Flatten Z Thresholding Direction: No theresholding ⁇ Find Threshold for: the whole image ⁇ Flatten Z Threshold %: 0.00% ⁇ Mark Excluded Data: Yes ⁇ Particle Analysis mode setting> (Detect tab) ⁇ Threshold Height: -2.00nm ⁇ Feature Direction: Below ⁇ X Axis: Absolute ⁇ Number Histogram Bins: 512 ⁇ Histogram Filter Cutoff: 0.00 nm ⁇ Min Peak to Peak: 1.00 nm ⁇ Left Peak Cutoff: 0.00000% ⁇ Right Peak Cutoff: 0.00000% (Modify tab) ⁇ Boughbirhood
  • the number of valley regions having a height of -2 nm or less from the reference plane in the above (1a) and the average of the valley regions having a height of -2 nm or less from the reference plane in the above (2a) The cross-sectional area shows that the surface of the biaxially oriented polyester film is densely formed with valley regions that are concave portions.
  • the surface A of the biaxially oriented polyester film and the surface B opposite to the surface A in the thickness direction are wound up with a configuration in which a smooth resist-uncoated surface, which will be described later, is formed. Even if the convex mountain areas are deformed by pressure and come into close contact with the smooth film surface or metal roll, even if they come into contact with metal rolls during transportation during the resist molding process, they will not form concave areas.
  • the valley region reduces the contact area, making it possible to ensure slipperiness.
  • the slipperiness may decrease because it is not sufficient to suppress the smooth film surface or adhesion with the metal roll. If the number is more than 500 pieces/5 ⁇ m square, the uniformity of the shape of the molded resist may be impaired.
  • the number of valley regions having a height of ⁇ 2 nm or less from the reference plane is preferably 150/5 ⁇ m or more, more preferably 200/5 ⁇ m or more, and still more preferably 300/5 ⁇ m or more.
  • the number of valley regions having a height of ⁇ 2 nm or less from the reference plane is preferably 480 pieces/5 ⁇ m ⁇ or less, more preferably 460 pieces/5 ⁇ m ⁇ or less, and even more preferably 450 pieces/5 ⁇ m ⁇ or less.
  • the average cross-sectional area of the valley region at a height of ⁇ 2 nm or less from the reference plane is less than 2000 nm 2 , it may not be sufficient to suppress adhesion to the metal roll, and the slipperiness may decrease. If the average cross-sectional area of the valley region at a height of ⁇ 2 nm or less from the reference plane is larger than 8000 nm 2 , the uniformity of the shape of the molded resist may be impaired.
  • the average cross-sectional area of the valley region at a height of ⁇ 2 nm or less from the reference plane is preferably 3000 nm 2 or more, more preferably 3400 nm 2 or more, and still more preferably 4000 nm 2 or more.
  • the average cross-sectional area of the valley region at a height of ⁇ 2 nm or less from the reference plane is preferably 7500 nm 2 or less, more preferably 7000 nm 2 or less, and still more preferably 6500 nm 2 or less.
  • the method for forming the uneven shape on the film surface is not particularly limited, but examples include a method of transferring the shape to the surface using a mold like nanoimprint, corona treatment using UV irradiation or arc discharge, plasma treatment using glow discharge, etc. surface treatment.
  • UV irradiation, corona treatment using arc discharge, and plasma treatment using atmospheric pressure glow discharge are preferable, as they ensure uniformity of treatment and less damage to the film.
  • Plasma treatment using atmospheric pressure glow discharge is more preferred.
  • Atmospheric pressure here is in the range of 700 Torr to 780 Torr.
  • a film to be treated is introduced between opposing electrodes and a ground roll, a plasma-excitable gas is introduced into the device, and a high-frequency voltage is applied between the electrodes to excite the gas into plasma. Glow discharge occurs between the electrodes. As a result, the surface of the film is finely ashed and protrusions are formed.
  • a plasma-excitable gas refers to a gas that can be plasma-excited under the conditions described above.
  • the plasma-excitable gas 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.
  • the number and average cross-sectional area of valley regions having a height of -2 nm or less from the reference plane of the film surface can be controlled within the above ranges by adding water vapor to the plasma-excitable gas and controlling the humidity.
  • water vapor By adding water vapor to the plasma-excitable gas, active species H * and OH * are generated, promoting the extraction of H elements from the molecular chains on the surface of the polyester film, and ashing deeply inward from the film surface.
  • a deep valley region which is a concave portion, is formed.
  • the amount of water vapor added to the plasma-excitable gas is controlled by the temperature and humidity of the plasma-excitable gas, and can be adjusted by controlling the humidity according to a temperature suitable for the process temperature.
  • the amount of water vapor contained in the plasma excitable gas is preferably 5 g/m 3 or more and 130 g/m 3 or less, and a more preferable lower limit is 20 g/m 3 or more.
  • the amount of water vapor contained in the plasma-excitable gas is 5 g/m 3 or more, ashing from the film surface to the inside can sufficiently proceed, and insufficient formation of valley regions can be suppressed.
  • the amount of water vapor contained in the plasma-excitable gas is 130 g/ m3 or less, it is possible to suppress the progress of excessive ashing on the entire film surface and prevent the reduction of the valley area. It is possible to suppress the occurrence of dew condensation and ensure stable processing.
  • the frequency of the high frequency voltage in plasma treatment is preferably in the range of 1 kHz to 100 kHz.
  • the discharge treatment intensity (E value) determined by the following method is preferably in the range of 10 to 2000 W ⁇ min/m 2 from the viewpoint of protrusion formation, more preferably 100 to 500 W ⁇ min/m 2 , More preferably, it is 200 to 400 W ⁇ min/m 2 . If the discharge treatment strength (E value) is too low, protrusions may not be formed sufficiently, and if the discharge treatment strength (E value) is too high, the film will be damaged or ashing will progress, which is not desirable. Protrusions may not be formed. Preferable protrusions can be formed by controlling the intensity of the discharge treatment depending on the amount of water vapor contained in the plasma-excitable gas and the intrinsic viscosity (IV) of the treated surface resin, which will be described later.
  • E value Vp ⁇ Ip/(S ⁇ Wt)
  • Vp Applied voltage
  • Ip Applied current
  • S Processing speed (m/min)
  • Wt processing width (m)
  • the surface temperature of the film at the time of surface treatment is 150° C. or less.
  • the temperature is more preferably 100°C or lower, most preferably 50°C or lower.
  • the surface temperature of the film at the time of surface treatment is 150° C. or lower, crystallization of the film is suppressed, formation of coarse protrusions on the surface is prevented, and ashing can proceed satisfactorily.
  • the surface temperature should be 10°C or higher, more preferably 15°C or higher, and even more preferably 25°C or higher. is preferred.
  • the surface treatment temperature can be adjusted by cooling the surface opposite to the treated surface with a cooling roll or the like.
  • the intrinsic viscosity (IV) of the resin of the layer constituting the surface to be surface treated is 0.45 dl/g or more and 0.70 dl/g or less. It is preferable that there be. IV is a number that reflects the length of the molecular chain, and the shorter the molecular chain, the easier it is for polyester molecules to orient and crystallize during stretching and heat treatment, so IV (dl/g) should be 0.70 dl/g or less. By doing so, it is possible to promote the formation of protrusions in the biaxial stretching film forming process and improve slipperiness.
  • the short molecular chains increase the molecular mobility of the surface, so when it comes into contact with a laminating roll heated to a temperature of 90 to 120 degrees Celsius, the surface softens and becomes easier to follow the roll. This can suppress wrinkles and air bubbles during lamination.
  • IVP1 0.45 dl/g or more, it is easy to clearly form crystalline parts and amorphous parts in the same molecular chain, so it is possible to form finer protrusions by atmospheric pressure glow discharge treatment. This is preferred because it is easy.
  • the intrinsic viscosity (IV) of the resin of the layer constituting the surface to be surface treated is more preferably 0.50 dl/g or more and 0.60 dl/g or less, and 0.50 dl/g or more and 0.60 dl/g or less. More preferably 55 dl/g or more and 0.60 dl/g or less.
  • the biaxially oriented polyester film of the second embodiment has the respective element concentrations C1s-A, O1s-A and N1s-A obtained by XPS measurement of at least one surface A', and the thickness from the surface layer of the surface A'.
  • the thickness removed by argon etching is confirmed by measuring the thickness before and after argon etching through cross-sectional observation using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the O element concentration of the surface A' is O1s-A/O1s-B>1.000, ashing by atmospheric pressure plasma treatment using the plasma-excitable gas containing water vapor is sufficiently promoted, resulting in a smooth surface. Improves slipperiness on film surfaces and metal rolls.
  • the O element concentration on the surface A' of the biaxially oriented polyester film is more preferably O1s-A/O1s-B ⁇ 1.010, and even more preferably O1s-A/O1s-B ⁇ 1.020.
  • the upper limit of O1s-A/O1s-B is not particularly limited, but is usually preferably 5.000 or less.
  • the amount of water vapor contained in the plasma excitable gas is set to 5 g/ m3 or more, and the discharge It is preferable to perform the treatment at a treatment intensity (E value) of 10 to 2000 W ⁇ min/m 2 , more preferably, the amount of water vapor contained in the plasma excitable gas is 20 g/m 3 or more, and the discharge treatment intensity (E value) ) It is preferable to perform the treatment in the range of 50 to 500 W ⁇ min/m 2 , more preferably in the range of 100 to 400 W ⁇ min/m 2 .
  • the surface A' of the biaxially oriented polyester film of the second embodiment was observed in the following (1a) and (2a) when observed with an AFM with a 5 ⁇ m square field of view under the condition I described above in the section (first embodiment). It is preferable that surface A satisfies the following. If the surface A′ of the second embodiment is a surface A, such surface A is similar to the surface A described above in the section of the first embodiment.
  • the number of valley regions with a height of -2 nm or less from the reference plane is 100 pieces/5 ⁇ m or more, and 500 pieces/5 ⁇ m or less
  • the average cross-sectional area of the valley regions with a height of -2 nm or less from the reference plane is 2000nm 2 or more, 8000nm 2 or less
  • the number of mountain regions with a height of +3 nm or more from the reference surface is 50 / 5 ⁇ m or more, 200 / It is preferably 5 ⁇ m ⁇ or less.
  • the average cross-sectional area of the peak region at a height of +3 nm or more from the reference plane is 3000 nm 2 or more and 7000 nm. It is preferably 2 or less.
  • ⁇ AFM measurement method> ⁇ Device: Bruker Atomic Force Microscope (AFM) Dimention Icon with ScanAsyst ⁇ Cantilever: Silicon nitride probe ScanAsyst Air ⁇ Scanning mode: ScanAsyst ⁇ Scanning speed: 0.977Hz ⁇ Scanning direction: Scan in the width direction of the measurement sample prepared by the method described below ⁇ Measurement field of view: 5 ⁇ m square ⁇ Sample line: 512 ⁇ Peak Force SetPoint: 0.0195V to 0.0205V ⁇ Feedback Gain: 10-20 ⁇ LP Deflection BW: 40kHz ⁇ ScanAsyst Noise Threshold: 0.5nm ⁇ Sample preparation: 23°C, 65%RH, left standing for 24 hours ⁇ AFM measurement environment: 23°C, 65%RH ⁇ Measurement sample preparation method: Paste double-sided tape on one side of an AFM sample disk (d
  • the surface opposite to the surface is pasted together to form a measurement sample.
  • - Number of sample measurements Measure 20 times at different locations so that each sample is separated by at least 5 ⁇ m.
  • ⁇ Measurement values Analyze the images of the 20 measured locations, measure each numerical value, and treat the average value as each numerical value of the sample.
  • the film surface image obtained by the above ⁇ AFM measurement method> is analyzed using the attached analysis software (NanoScope Analysis Version 1.40). Flatten processing is performed on the obtained height sensor image of the film surface.
  • the reference plane is a plane with a height of 0 nm determined under the Flatten processing conditions described below.
  • the Mean values of Total Count and Area which are calculated by setting the items of the Detect tab in the Particle Analysis analysis mode as shown below, are respectively the number of mountain regions with a height of +3 nm or more from the reference plane and the average cross-sectional area.
  • the number of peak regions with a height of +3 nm or more from the reference surface is 50/5 ⁇ m or more and 200/5 ⁇ m or less, indicating that protrusions are densely formed on the surface of the biaxially oriented polyester film.
  • the number of mountain regions with a height of +3 nm or more from the reference surface is 50/5 ⁇ m or more, the increase in the area where the films come into close contact with each other is suppressed when the biaxially oriented polyester film is wound into a roll in the manufacturing process. This can reduce frictional force and improve slipperiness. Since the number of mountain regions with a height of +3 nm or more from the reference surface is 200 pieces/5 ⁇ m or less, when the biaxially oriented polyester film of the present invention is used as an ultraviolet light irradiation surface during resist molding, ultraviolet light can penetrate inside the film. It is possible to suppress scattering on the surface and improve the uniformity of the resist shape.
  • the number of mountain regions having a height of +3 nm or more from the reference plane is preferably 50 pieces/5 ⁇ m ⁇ or more, and more preferably 70 pieces/5 ⁇ m ⁇ or more.
  • the average cross-sectional area of the mountain region with a height of +3 nm or more from the reference plane is 3000 nm 2 or more and 7000 nm 2 or less indicates that fine protrusions are formed.
  • the average cross-sectional area of the peak region By having an average cross-sectional area of the peak region at a height of +3 nm or more from the reference surface of 3000 nm2 or more, the increase in the area that comes into close contact with the metal roll in the resist forming process is suppressed, and the frictional force is reduced and slipperiness is improved. It can be improved.
  • the average cross-sectional area of the peak region By setting the average cross-sectional area of the peak region with a height of +3 nm or more from the reference surface to 7000 nm2 or less, when the biaxially oriented polyester film of the present invention is used as an ultraviolet light irradiation surface during resist molding, ultraviolet light will not penetrate inside the film or Scattering on the surface can be suppressed and the uniformity of the resist shape can be improved.
  • the average cross-sectional area of the mountain region having a height of +3 nm or more from the reference plane is preferably 3000 nm 2 or more, more preferably 3500 nm 2 or more, and still more preferably 4000 nm 2 or more. Further, the average cross-sectional area of the mountain region having a height of +3 nm or more from the reference plane is preferably 7000 nm 2 or less, more preferably 6800 nm 2 or less, and still more preferably 6500 nm 2 or less.
  • Examples of methods for bringing the number and average cross-sectional area of mountain regions with a height of +3 nm or more from the reference surface into the above range include a method of plasma treatment with a plasma-excitable gas containing water vapor, a method of plasma treatment with a plasma-excitable gas containing water vapor, and a method of treating the surface of a biaxially oriented polyester film. Examples include a method of incorporating particles into the liquid.
  • An embodiment of the biaxially oriented polyester film of the present invention has (1a) the number of valley regions with a height of -2 nm or less from the reference plane of 100 or more/5 ⁇ m ⁇ or less than 500/5 ⁇ m ⁇ , (2a) standards
  • the kurtosis is 2.0 or more and 10.0 or less when observing surface A with an AFM in a 5 ⁇ m square field of view, where the average cross-sectional area of the valley region at a height of -2 nm or less from the surface is 2000 nm 2 or more and 8000 nm 2 or less. It is preferable.
  • a kurtosis of 2.0 or more and 10.0 or less when observed with AFM in a 5 ⁇ m square field of view indicates that particles are substantially absent or present at an extremely low concentration on the surface of the biaxially oriented polyester film. It shows. Due to the fact that particles are substantially absent or present at an extremely low concentration on the surface of the biaxially oriented polyester film, the resist shape obtained when the biaxially oriented polyester film of the present invention is used as the surface irradiated with ultraviolet light during resist molding. uniformity can be improved. When particles are contained on the surface of the biaxially oriented polyester film of the present invention, it is preferable to control the particle diameter and particle concentration so that the kurtosis falls within the above range.
  • the biaxially oriented polyester film of the present invention preferably has a kurtosis of 2.0 or more, more preferably 2.5 or more, still more preferably 3.0 or more when surface A is observed with AFM in a 5 ⁇ m square field of view. be. Further, the kurtosis is preferably 10.0 or less, more preferably 8.0 or less, still more preferably 5.0 or less.
  • the biaxially oriented polyester film of the present invention has the respective element concentrations C1s-A, O1s-A, and N1s-A obtained by XPS measurement of the surface A, and the surface a etched to a thickness of 500 nm from the surface layer of the surface A.
  • Each element concentration C1s-a, O1s-B and N1s-a obtained by XPS measurement of surface a etched to a thickness of 500 nm from the surface layer of surface A is N1s-A/N1s-a ⁇ 2.000.
  • N element is added to the surface of the biaxially oriented polyester film by atmospheric pressure plasma treatment using the plasma-excitable gas. shows that they are connected.
  • the valley area on the surface of the biaxially oriented polyester film can be easily controlled within a preferable range, and a decrease in slipperiness during long-term storage can be suppressed.
  • nitrogen gas is used as the main component of the plasma excitable gas in the atmospheric pressure plasma treatment, and the discharge treatment intensity (E value) is adjusted to 10 to 2000 W. It is preferable to perform the plasma treatment at a power of min/m 2 , more preferably to perform the plasma treatment at a power of 50 to 500 W ⁇ min/m 2 , and even more preferably to perform the plasma treatment at a power of 100 to 400 W ⁇ min/m 2 .
  • the main component here refers to 50% by weight or more in the plasma excitable gas.
  • the biaxially oriented polyester film of the present invention has each element concentration C1s-A, O1s-A, and N1s-A measured by XPS on the surface, and XPS measured in the depth direction at an ion etching rate of 1.8 nm/min.
  • Each element concentration C1s-a, O1s-a and N1s-a preferably satisfies N1s-A/N1s-a ⁇ 2.000, more preferably N1s-A/N1s-a ⁇ 2.500.
  • the upper limit of N1s-A/N1s-a is not particularly limited, but it is usually preferably 10.000 or less.
  • the biaxially oriented polyester film of the present invention satisfies the following (1c) and (2c) when surface A and surface B opposite in the thickness direction are observed by ⁇ scanning white interference microscopy> under condition III below. It is preferable.
  • (1c) Arithmetic mean height is 0.5 nm or more and 2.0 nm or less
  • (2c) Maximum protrusion height is 20 nm or more and 150 nm or less
  • ⁇ Scanning white interference microscopy measurement method> A 6 cm x 6 cm sample was taken from the biaxially oriented polyester film, and each sample was examined using a scanning white interference microscope (equipment: "VertScan” (registered trademark) VS1540 manufactured by Hitachi High-Tech Science Co., Ltd.). Surface B is measured using a 50x objective lens, the measurement mode is set to WAVE mode, and 90 visual fields are measured with a measurement area of 113 ⁇ m ⁇ 113 ⁇ m. The sample set is measured by setting the sample on a stage so that the measurement Y-axis is in the longitudinal direction of the sample film (the direction in which the film is wound).
  • ISO parameter analysis processing is performed under the following conditions.
  • ⁇ S-Filter Automatic/Normal probability paper Number of divisions: 300 Upper limit of calculation range: 3.000 Lower limit of calculation range: -3.000 - Parameters: Select "Height Parameters” - Output: Select "Parameter List”.
  • the arithmetic mean height of surface A and surface B facing each other in the thickness direction is 0.5 nm or more and 2.0 nm or less indicates that the surface roughness of surface B, which is a resist-uncoated surface, is controlled. .
  • the transportability in the manufacturing process of the biaxially oriented polyester film of the present invention can be improved.
  • the slipperiness in the resist molding process is improved and the uniformity of the resist shape obtained. can be increased.
  • the arithmetic mean height of surface B of the biaxially oriented polyester film of the present invention there is a method of containing particles in the layer constituting surface B (P2 layer). It is preferable to control the particle diameter and particle concentration so that the arithmetic mean height falls within the above range.
  • the surface of the biaxially oriented polyester film is prevented from becoming extremely smooth, and the biaxially oriented polyester film of the present invention can be produced. It is possible to suppress a decrease in slipperiness during the process and a decline in slipperiness against a metal roll in the resist forming process.
  • the arithmetic mean height of the surface A and the surface B facing each other in the thickness direction is preferably 0.5 nm or more, more preferably 0.7 nm or more, and still more preferably 0.9 nm or more. Further, the arithmetic mean height is preferably 2.0 nm or less, more preferably 1.8 nm or less, still more preferably 1.6 nm or less.
  • the maximum protrusion height of surface B which faces surface A in the thickness direction, is 20 nm or more and 150 nm or less indicates that the surface roughness of surface B, which is a non-resist coated surface, is controlled and does not contain coarse particles. It shows.
  • the slipperiness in the resist molding process is improved and the uniformity of the resist shape obtained. can be increased.
  • a method for making the maximum protrusion height of the surface B of the biaxially oriented polyester film of the present invention within the above range there is a method of containing particles in the layer (P2 layer) constituting the surface B. In this case, it is preferable to control the particle diameter, particle concentration, and thickness of the layer (P2 layer) constituting surface B so that the maximum protrusion height falls within the above range.
  • the surface of the biaxially oriented polyester film is prevented from becoming extremely smooth, and in the manufacturing process of the biaxially oriented polyester film of the present invention. It is possible to suppress a decrease in slipperiness, a decrease in winding quality when winding into a roll, and a decrease in slipperiness against a metal roll in the resist forming process.
  • the maximum protrusion height of surface B opposite to surface A in the thickness direction is 150 nm or less, coarse irregularities on the surface of the biaxially oriented polyester film are reduced, and surface B of the biaxially oriented polyester film of the present invention can be resist-molded.
  • the surface is sometimes irradiated with ultraviolet light, scattering of the ultraviolet light inside or on the surface of the film can be suppressed to improve the uniformity of the resist shape.
  • the maximum protrusion height of surface B that faces surface A in the thickness direction is preferably 20 nm or more, more preferably 50 nm or more. Further, the maximum protrusion height is preferably 150 nm or less, more preferably 130 nm or less.
  • the biaxially oriented polyester film of the present invention was observed by observing the surface A and the surface B opposite to the surface A in the thickness direction using the ⁇ scanning white interference microscopy method> under the above condition III. It is preferable that the skewness Ssk-A and the skewness Ssk-B calculated by -Calculation of B satisfy the following (1d), (2d), and (3d).
  • (1d) Ssk-A is -0.1 or more and 1.0 or less
  • Ssk-B is 1.0 or more and 4.0 or less
  • (3d) Ssk-B -Ssk-A is 0.1 or more and 3.0 or less
  • Skewness Ssk generally indicates the symmetry of the distribution of peaks and valleys in the surface shape.
  • Ssk 0, the distribution of peaks and valleys is vertically symmetrical, and when Ssk > 0, the distribution of peaks and valleys is symmetrical. This indicates that there are many valleys, and when Ssk ⁇ 0, there are many valleys.
  • the skewness Ssk-A of the surface A is -0.1 or more and 1.0 or less indicates that minute protrusions (mountains) are formed on the surface A. There is.
  • the skewness of the surface A of the biaxially oriented polyester film within the above range, when the surface A of the biaxially oriented polyester film of the present invention is used as a resist coated surface during resist molding, the unevenness of the surface A is transferred to the resist.
  • the uniformity of the resist shape can be improved and the occurrence of resist defects can be suppressed.
  • skewness Ssk-A of surface A is subjected to atmospheric pressure glow discharge treatment using the plasma-excitable gas containing water vapor described above to form microprotrusions.
  • This can be achieved by having the skewness Ssk-A of the surface A of -0.1 or more, the surface A of the biaxially oriented polyester film is prevented from becoming extremely smooth, and the skewness Ssk-A of the biaxially oriented polyester film of the present invention is prevented from becoming extremely smooth. It is possible to suppress a decrease in slipperiness and a decrease in winding quality when winding into a roll.
  • the skewness Ssk-A of surface A is 1.0 or less, which prevents the formation of many large protrusions on surface A of the biaxially oriented polyester film, improves shape uniformity during resist formation, and suppresses the occurrence of resist defects. can.
  • the average primary particle diameter of the particles is preferably 100 nm or less, more preferably 70 nm or less. By having an average primary particle diameter of 100 nm or less, it is possible to prevent the skewness Ssk-A from becoming larger than 1.0, and to suppress the transfer of unevenness to the resist and the decrease in the uniformity of the resist shape.
  • the content of particles contained in the layer constituting surface A is preferably 0.7% by mass or less, and 0.3% by mass or less based on the mass of the entire layer constituting surface A (P1 layer). It is preferable that there be.
  • the surface A skewness Ssk-A of the biaxially oriented polyester film of the present invention is preferably -0.1 or more, more preferably 0.0 or more, and still more preferably 0.1 or more. Further, the skewness Ssk-A is preferably 1.0 or less, more preferably 0.7 or less, still more preferably 0.5 or less.
  • the skewness Ssk-B of the surface A and the surface B facing each other in the thickness direction is 1.0 or more and 4.0 or less.
  • the skewness increases or decreases depending on the content of the particles and the particle size of the largest particle among the contained particles.
  • the fact that the skewness Ssk-B is 1.0 or more and 4.0 or less indicates that the distribution (number, height, length) of protrusions (crests) on the surface B is controlled, and the skewness Ssk-B is 1.0 or more and 4.0 or less.
  • the average primary particle content of the particles contained in the P2 layer is This can be achieved by controlling the diameter and the thickness of the P2 layer.
  • the average primary particle size of the particles having the largest average primary particle size among the particles contained in the layer constituting surface B is 50 nm or more and 250 nm or less, more preferably 100 nm or more and 200 nm or less. If the average primary particle size of the particles with the largest average primary particle size among the particles contained in the P2 layer is 50 nm or more, the skewness Ssk-B can be prevented from becoming less than 1.0, and the slippage with the film or metal roll can be prevented. It can suppress the decline in sexual performance.
  • the average primary particle size of the particles with the largest average primary particle size among the particles contained in the P2 layer is too large, the content of the particles with the largest average primary particle size among the particles contained in the P2 layer, which will be described later, Even if the thickness of the P2 layer is adjusted, the skewness Ssk-B may become larger than 4.0, and if the surface is irradiated with ultraviolet light during the resist shape, the ultraviolet light will be scattered inside and on the film surface, causing the resist shape to deteriorate. uniformity may be impaired.
  • the average primary particle diameter here refers to that determined under the following conditions. Observe the cross section of the film at a magnification of 10,000 times using a transmission electron microscope (TEM). At this time, if particles of 1 cm or less are confirmed on the photograph, the TEM observation magnification is changed to 50,000 times and observed. The section thickness of the TEM was approximately 100 nm, and 100 fields of view were measured at different locations. The equivalent circular diameter was determined for all the dispersed particles photographed. The horizontal axis represents the equivalent circular diameter, and the vertical axis represents the equivalent circular diameter of the particles. The number distribution of particles was plotted as the number of particles, and the equivalent circular equivalent diameter of the peak value was taken as the average primary particle diameter of the particles.
  • TEM transmission electron microscope
  • the number distribution of the equivalent circle diameter is a distribution having two or more peaks.
  • the equivalent circular equivalent diameter of each peak value is taken as the average primary particle diameter of each particle.
  • Measuring device Transmission electron microscope (TEM) Hitachi model H-7100FA Measuring conditions: Accelerating voltage 100kV Measurement magnification: 10,000 times, 50,000 times Sample preparation: Ultra thin film section method Observation surface: TD-ZD cross section (TD: width direction, ZD: thickness direction)
  • Either inorganic particles or organic particles may be used as the particles having the largest average primary particle diameter among the particles contained in the P2 layer.
  • inorganic particles include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, mica, mica, titanium mica, zeolite, talc, clay, kaolin, Examples include lithium fluoride, calcium fluoride, montmorillonite, zirconia, wet silica, dry silica, and colloidal silica.
  • the content of particles with the largest average primary particle diameter among the particles contained in the P2 layer is 0.005% by mass or more and 0.030% by mass based on the entire weight of the P2 layer in order to achieve both resist properties and slipperiness. % or less, more preferably 0.008% by mass or more and 0.020% by mass or less. If the content of particles with the largest average primary particle diameter among the particles contained in the layer constituting surface B is less than 0.005% by mass, sufficient peaks will not be formed on the surface, resulting in skewness Ssk-B. is less than 1.0, and there is a possibility that the slipperiness with the film or metal roll may be impaired. If the content is more than 0.030% by mass, the skewness Ssk-B may become greater than 4.0, and there is a concern that the uniformity of the resist shape may deteriorate.
  • the thickness of the layer (P2 layer) including surface B is preferably 0.05 ⁇ m or more and 0.4 ⁇ m or less.
  • the thickness of the P2 layer is 0.05 ⁇ m or more, detachment of the contained particles is suppressed, and the formation of protrusions by the particles inside the P2 layer is sufficient, which can ensure slipperiness with the film and metal roll.
  • the thickness of the P2 layer is 0.4 ⁇ m or less, an increase in the total number of particles contained in the P2 layer can be suppressed, and wobbling in the resist shape can be prevented.
  • the thickness of the P2 layer included in the surface B is more preferably 0.10 ⁇ m or more and 0.35 ⁇ m or less, and even more preferably 0.15 ⁇ m or more and 0.30 ⁇ m or less.
  • the skewness Ssk-B of the surface A and the surface B facing each other in the thickness direction of the biaxially oriented polyester film of the present invention is preferably 1.0 or more, more preferably 1.2 or more, and even more preferably 1.5. That's all. Further, the skewness Ssk-B is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.
  • the skewness difference (Ssk-B)-(Ssk-A) between surface A and surface B of the biaxially oriented polyester film of the present invention is preferably 0.1 or more and 3.0 or less.
  • the difference in skewness between surfaces A and B indicates that the difference in shape between surfaces A and B is small after Ssk-A and Ssk-B are controlled as described above.
  • (Ssk-B)-(Ssk-A) is 0.1 or more, the formation of protrusions on the surface B is sufficient, and the slipperiness with the film or metal roll can be ensured.
  • the surface shapes of surface A and surface B can be This can be achieved by controlling the
  • the skewness Ssk difference (Ssk-A)-(Ssk-B) between surface A and surface B of the biaxially oriented polyester film of the present invention is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0. .5 or more.
  • the skewness difference (Ssk-B)-(Ssk-A) is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less.
  • the number of coarse particles with a major diameter of 2.0 ⁇ m or more existing in a region of 3 ⁇ m in the film thickness direction observed from the surface B side with an optical microscope is set as N (pieces/8.25 mm 2 ). In this case, it is preferable that N be 20 or less.
  • the long axis here refers to the longest major axis dimension of a rectangular parallelepiped circumscribing the projected view of the large object in an image of the large object obtained when the film is observed perpendicularly from the surface B side.
  • the range of N (pieces/8.25 mm 2 ) is preferably 10 or less, more preferably 8 or less.
  • the method of setting the preferable range of N is a method that uses a polymer melted and extruded with an extruder. This is a method of filtering the information using a filter. Particles contained in the biaxially oriented polyester film, catalyst residues from the polymerization of the polyester resin, and very small foreign matter that enter the film from outside the film forming process will cause coarse protrusion defects if they enter the film. It is effective to use a highly accurate one that can capture 95% or more of foreign particles with a diameter of 5 ⁇ m or more. Furthermore, when particle master pellets are used to incorporate particles into the biaxially oriented polyester film of the present invention, it is more preferable to use a similar filter when preparing the particle master pellets.
  • a highly concentrated particle master pellet is made in advance, and the particles are added during film formation.
  • An effective method is to adjust the particle content by diluting the particles with a polyester resin that does not substantially contain the particles.
  • the intrinsic viscosity of the polyester resin that does not contain particles is reduced. It is possible.
  • the intrinsic viscosity of the particle master pellet is higher than or the same as that of the polyester resin that does not contain particles, the dispersibility of particles decreases and the distance between particles becomes shorter, resulting in larger particle aggregates.
  • coarse particles with a major diameter of 2.0 ⁇ m or more to increase in the above-mentioned region of 3 ⁇ m in the film thickness direction.
  • the particle content of the particle master pellet used to contain the particles of the biaxially oriented polyester film of the present invention is as follows: It is preferably 0.5% by mass or less, more preferably 0.3% by mass or less based on the weight of the master pellet. If the particle content of the particle master pellet, which is the particle with the largest particle size among the particles added to the layer constituting surface B, is 0.5% by mass or less, the polyester resin does not substantially contain particles during film formation. When added to and dispersed in a film, it is possible to suppress an increase in the number of coarse particles having a major axis of 2.0 ⁇ m or more existing in the above-mentioned region of 3 ⁇ m in the film thickness direction due to particle aggregation.
  • the particle content of the particle master pellet used when containing the particles of the biaxially oriented polyester film of the present invention is as follows:
  • the amount is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, based on the weight of the particle master pellet.
  • the width direction (TD direction) when the film dimensional change rate is ⁇ L90-130°C (ppm/°C) when the film temperature is raised from 90°C to 130°C, the width direction (TD direction), It is preferable that at least one direction in the longitudinal direction (MD direction) is -50 or more and 150 or less.
  • the film dimensional change rate ⁇ L90-130°C (ppm/°C) when the film temperature is raised from 90°C to 130°C is a value obtained by thermomechanical analysis (TMA) measurement described below.
  • TMA thermomechanical analysis
  • This is a value representing the dimensional change rate when the biaxially oriented polyester film of the present invention is heated with a high-temperature laminating roll in the lamination process, and if the value is positive, it will expand, and if the value is negative, it will shrink. It is a value that represents By setting the ⁇ L90-130°C (ppm/°C) to -50 or more, the thermal shrinkage can be reduced to an appropriate range.
  • the biaxially oriented polyester film undergoes greater heat shrinkage than the conventional resist layer, causing curling on the biaxially oriented polyester side and causing the resist layer to peel off from the copper foil substrate that is in close contact with it.
  • lifting may occur between the copper foil substrate and the resist layer, but this can be suppressed in the present invention.
  • the lower limit of ⁇ L90-130°C (ppm/°C) is more preferably 0 or more.
  • the thermal expansion can be reduced to an appropriate range.
  • the biaxially oriented polyester film expands more than the conventional resist layer, which causes the resist layer attached to the biaxially oriented polyester film to be stretched excessively, causing minute defects in the resist layer.
  • lifting may occur between the copper foil substrate and the resist layer starting from this point, but the present invention can suppress this.
  • the upper limit of ⁇ L90-130°C (ppm/°C) is more preferably 100 or less.
  • heat treatment and relaxation treatment in the width direction are carried out in the transverse stretching step when forming a biaxially stretched polyester film, which will be described later.
  • This can be achieved by subjecting the biaxially stretched film to a heat treatment at a temperature above a certain temperature and at the same time subjecting it to relaxation treatment at a temperature above a certain temperature.
  • the laminated polyester film is heat treated at a temperature of 221°C or more and 240°C or less, and at the same temperature as the heat treatment temperature, a relaxation treatment is performed at a rate of 1% or more and 4% or less in the width direction.
  • a relaxation treatment is performed at a rate of 1% or more and 4% or less in the width direction.
  • a more preferable range of the heat treatment temperature is 225°C or more and 240°C or less, most preferably 230°C or more and 240°C or less. Further, as a preferable range of the ratio of relaxation treatment in the width direction performed at the heat treatment temperature, the lower limit is more preferably 1.5% or more, and the upper limit is more preferably 2.5% or less.
  • the relaxation treatment in the width direction was performed. After that, it is preferable to perform a relaxation treatment in the width direction at a temperature of 90° C. or more and 150° C. or less, which corresponds to the laminating temperature range, at a rate of 0.5% or more and 3% or less. This is because by performing the relaxation treatment in the width direction at the above temperature, the polyester resin molecular chains within the film take on a stable structure at the lamination processing temperature.
  • the relaxation treatment method performed at a temperature of 90°C or more and 150°C or less, it is more preferable to perform the relaxation treatment in the width direction two or more times in two different temperature ranges, and at a temperature of 115°C or more and 150°C or less.
  • Relaxation treatment is performed in the width direction at a rate of 0.5% or more and 2.0% or less, and then relaxation treatment is performed in the width direction at a rate of 0.3% or more and 2.0% or less at a temperature of 90°C or more and less than 115°C.
  • the lower limit of the ratio of relaxation treatment in the width direction (relaxation treatment) performed at a temperature of 115° C. or higher and 150° C. or lower is more preferably 1.0% or more, and the upper limit is more preferably 1.8% or less. .
  • the lower limit is more preferably 0.5% or more, and the upper limit is more preferably 1.5% or less. , more preferably 0.8% or less.
  • the total percentage of relaxation treatments performed at each temperature after the heat treatment is 5% or less.
  • the total relaxation treatment ratio is 4.5% or less.
  • the ⁇ L90-130°C (ppm/°C) is -50 or more and 150 or less.
  • a more preferable form is that the direction is the width direction (TD direction) of the roll during lamination.
  • the biaxially oriented polyester film of the present invention can be suitably used as a film for a dry film resist support.
  • the surface is observed with AFM in a 5 ⁇ m square field of view, at least one surface has (1a) the number of valley regions with a height of -2 nm or less from the reference surface of 100 pieces/5 ⁇ m ⁇ or more, and 500 pieces/5 ⁇ m ⁇ or less, (2a)
  • a biaxially oriented polyester film which is surface A, where the average cross-sectional area of the valley region at a height of -2 nm or less from the reference plane satisfies 2000 nm 2 or more and 8000 nm 2 or less as a resist coating surface during resist molding. , it exhibits excellent sliding properties on metal rolls during the manufacturing process without impairing the uniformity of the resist shape, and can also improve the winding performance when winding into a roll.
  • the biaxially oriented polyester film of the present invention can be suitably used as a support film for green sheet molding in the process of manufacturing a multilayer ceramic capacitor.
  • the surface is observed with AFM in a 5 ⁇ m square field of view, at least one surface has (1a) the number of valley regions with a height of -2 nm or less from the reference surface of 100 pieces/5 ⁇ m ⁇ or more and 500 pieces/5 ⁇ m ⁇ or less, (2a)
  • a biaxially oriented polyester film which is surface A, where the average cross-sectional area of the valley region at a height of -2 nm or less from the reference plane satisfies 2000 nm 2 or more and 8000 nm 2 or less, as the ceramic slurry coating surface, the ceramic layer It exhibits excellent sliding properties on metal rolls in the manufacturing process without transferring unevenness to the surface, and can improve the winding performance when winding into a roll.
  • the biaxially oriented polyester film of the present invention includes a layer containing surface A (P1 layer) and a layer facing the P1 layer (P2 layer), and has two or more layers in which the P1 layer and the P2 layer are arranged on the outermost surface.
  • the structure (P1 layer/P2 layer or P1 layer/P3 layer/P2 layer structure) is preferable.
  • a three-layer structure is preferred from the viewpoint of achieving both optical properties and slipperiness by adjusting the amount of particles added in each layer.
  • the method of laminating other resin layers such as the P1 layer, P2 layer, and P3 layer is not particularly limited, but examples include the coextrusion method described below, and the method of adding other resin layer raw materials to the film in the middle of film formation into an extruder. Examples include a method of melt-extruding the film and laminating it while extruding it from a die (melt lamination method), and a method of laminating the films after film formation with an adhesive layer interposed therebetween. Among these, the coextrusion method is preferred because it allows the formation of protrusions by the above-mentioned surface treatment and lamination at the same time.
  • each layer may contain particles within a range that does not impair the characteristics of the present invention.
  • the biaxially oriented polyester film of the present invention may contain particles, it may contain organic particles, inorganic particles, or both.
  • the biaxially oriented polyester film of the present invention preferably has a thickness of 10 ⁇ m or more and 500 ⁇ m or less, more preferably 10 ⁇ m or more and 40 ⁇ m or less. Particularly preferably, the thickness is 15 ⁇ m or more and 20 ⁇ m or less.
  • the thickness is 15 ⁇ m or more and 20 ⁇ m or less.
  • the intrinsic viscosity (IV) of the biaxially oriented polyester film of the present invention is preferably 0.45 or more, more preferably 0.50 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 crystalline and amorphous parts within the same molecular chain. This is preferred because it facilitates the formation of fine protrusions.
  • the surface free energy (mN/m) of the surface A of the biaxially oriented polyester film of the present invention is preferably 40 or more and 48 or less, more preferably 43 or more and 45 or less.
  • the surface free energy (mN/m) is 40 or more and 48 or less, it is possible to improve the adhesion when laminating another layer on the A side and suppress the occurrence of defects.
  • the film forming method described below which includes a step of subjecting the film surface to atmospheric pressure glow discharge treatment and then heat treatment, the functional groups formed by ashing by atmospheric pressure glow discharge treatment lose their activity through heat treatment, thereby improving the surface free energy. It can be a range.
  • the biaxially oriented polyester film of the present invention preferably has a tear propagation resistance of 4,500 mN/mm or more and 10,000 mN/mm or less in the longitudinal direction and the width direction, which are the film forming line directions.
  • the tear propagation resistance in the longitudinal direction and the width direction is more preferably 4500 mN/mm or more and 8000 mN/mm or less, and even more preferably 5000 mN/mm or more and 7000 mN/mm or less.
  • the area magnification (stretching ratio in the longitudinal direction x stretching ratio in the width direction) during production of the biaxially oriented polyester film is preferably 10 times or more and 25 times or less.
  • heat treatment is performed, and the temperature of the heat treatment can be controlled by setting the temperature at which the polyester is used (melting point -40° C.) or higher and lower than the melting point.
  • a conventional polymerization method can be used to obtain the polyester used in the present invention.
  • a dicarboxylic acid component such as terephthalic acid or its ester-forming derivative is transesterified or esterified with a diol component such as ethylene glycol or its ester-forming derivative by a known method, and then a melt polymerization reaction is performed. You can get it by doing. Further, if necessary, the polyester obtained by the melt polymerization reaction may be subjected to a solid phase polymerization reaction at a temperature below the melting point temperature of the polyester.
  • the polyester film in the present invention can be obtained by conventionally known manufacturing methods, but by manufacturing the stretching and heat treatment steps under the following conditions, at least one surface can be made into surface A having the preferable physical properties as described above. I can do it.
  • a method for manufacturing the polyester film in the present invention for example, if necessary, a method (melt casting method) in which dried raw materials are heated and melted in an extruder and extruded from a die onto a cooled cast drum to form a sheet.
  • Other methods include, for example, dissolving the raw material in a solvent, extruding the solution from a die onto a support such as a cast drum or endless belt to form a film, and then drying and removing the solvent from the film layer to form a sheet.
  • a processing method (solution casting method), etc. may also be mentioned.
  • an extruder is used for each layer constituting the laminated polyester film, the raw materials for each layer are melted, and the raw materials for each layer are melted and transferred to a confluence between the extrusion device and the die.
  • a preferred method is to stack the materials in a molten state in an apparatus, introduce them into a die, extrude them from the die onto a cast drum, and process them into a sheet to obtain a laminated sheet.
  • the laminated sheet processed into a sheet is cooled and solidified by static electricity on a cast drum whose surface temperature is preferably cooled to 20° C. or higher and 60° C. or lower to produce an unstretched sheet.
  • the temperature of the cast drum is more preferably 25°C or more and 60°C or less, and even more preferably 40°C or more and 55°C or less.
  • the unstretched sheet is subjected to surface treatment.
  • the surface treatment include methods such as nanoimprinting in which a shape is transferred to the surface using a mold, corona treatment using ultraviolet light irradiation or arc discharge, plasma treatment using glow discharge, and the like. These surface treatments may be carried out immediately after obtaining the unstretched sheet, after slight stretching, or after stretching in the longitudinal and/or lateral directions, but in the present invention it is preferable to surface-treat the unstretched sheet.
  • the surface to be surface-treated may be either the surface that was in contact with the cast drum (drum surface) or the surface that is not in contact with the cast drum (non-drum surface). At this time, the surface temperature of the film surface to be surface-treated is controlled so as not to become too high.
  • the stretching method include a sequential biaxial stretching method and a simultaneous biaxial stretching method.
  • a sequential biaxial stretching method in which stretching is performed first in the longitudinal direction and then in the width direction is preferred from the viewpoint of obtaining the biaxially oriented polyester film of the present invention without stretching tearing.
  • the area magnification (stretching ratio in the longitudinal direction x stretching ratio in the width direction) is preferably 10 times or more and 25 times or less, more preferably 12 times or more and 20 times or less.
  • the shape imparted to the unstretched film is subdivided, and a more desirable surface shape, especially the number of valley regions with a height of -2 nm or less from the reference plane, and the average cross-sectional area are set within a desirable range. It can be done.
  • the area magnification By setting the area magnification to 10 times or more, it is possible to prevent the valley region having a height of ⁇ 2 nm or less from the reference plane from decreasing or from decreasing the average cross-sectional area.
  • By setting the area magnification to 25 times or less tearing due to stretching can be suppressed.
  • the heat treatment temperature is preferably (melting point -40)°C or higher and lower than the melting point of the thermoplastic resin used, more preferably (melting point -40)°C or higher and (melting point -15)°C or lower.
  • thermoplastic resin used is a crystalline polyester such as PET or PEN
  • the shape is imparted to the unstretched film by the ashing effect of atmospheric pressure glow discharge treatment
  • the remaining crystalline portions are removed by the ashing treatment. It is divided into small parts by stretching, and then by heat treatment, crystals grow using the parts as nuclei, so that the protrusion shape can be made into a preferable shape.
  • the heat treatment temperature By setting the heat treatment temperature to a melting point of ⁇ 40° C. or higher, sufficient crystal growth is achieved. Melting of the protrusions can be suppressed by setting the heat treatment temperature to below the melting point.
  • ⁇ Flatten processing> The film surface image obtained under the above observation conditions is analyzed using the attached analysis software (NanoScope Analysis Version 1.40). The obtained height sensor image of the film surface is subjected to flatten processing.
  • the reference plane of the film surface is a plane with a height of 0 nm determined under the flatten processing conditions described above.
  • ⁇ Particle Analysis mode setting> (Detect tab) ⁇ Threshold Height: -2.00nm ⁇ Feature Direction: Below ⁇ X Axis: Absolute ⁇ Number Histogram Bins: 512 ⁇ Histogram Filter Cutoff: 0.00nm ⁇ Min Peak to Peak: 1.00nm ⁇ Left Peak Cutoff: 0.00000% ⁇ Right Peak Cutoff: 0.00000% (Modify tab) ⁇ Boughbirhood Size:3 ⁇ Number Pixels Off: 1 ⁇ Do not perform any Dilate/Erode operations.
  • the average values of the Total Count and Area Mean values at 20 locations are the number and average cross-sectional area of valley regions that are +3 nm or more from the height reference plane, respectively.
  • ⁇ Particle Analysis mode setting> (Detect tab) ⁇ Threshold Height: 3.00nm ⁇ Feature Direction: Above ⁇ X Axis: Absolute ⁇ Number Histogram Bins: 512 ⁇ Histogram Filter Cutoff: 0.00nm ⁇ Min Peak to Peak: 1.00nm ⁇ Left Peak Cutoff: 0.00000% ⁇ Right Peak Cutoff: 0.00000% (Modify tab) ⁇ Boughbirhood Size:3 ⁇ Number Pixels Off: 1 ⁇ Do not perform any Dilate/Erode operations.
  • Kurtosis is determined as the average value of 20 Kurtosis values calculated by setting each item of the tab and Peak Inputs tab as follows.
  • ⁇ Etching conditions in the depth direction> A thickness of 500 nm ⁇ 10 nm is removed by sputter etching from the surface A' of the biaxially oriented polyester film thermoplastic resin film using argon ions. The thickness removed by argon etching is confirmed by measuring the thickness before and after argon etching through cross-sectional observation using a transmission electron microscope (TEM). The obtained etched surface a is subjected to measurement of each element type under the same conditions as the XPS measurement conditions described above.
  • O element concentration ratio O1s-A/O1s-a From the O1s-A of the surface A obtained under the above XPS measurement conditions and data processing conditions and the O1s-a obtained by XPS measurement of the surface a etched to a thickness of 500 nm from the surface layer of the surface A, the O element concentration ratio is determined. Calculate O1s-A/O1s-a.
  • N element concentration ratio N1s-A/N1s-a From the N1s-A of the surface A obtained under the above XPS measurement conditions and data processing conditions and the N1s-a obtained by XPS measurement of the surface a etched to a thickness of 500 nm from the surface layer of the surface A, the N element concentration ratio is determined. Calculate N1s-A/N1s-a.
  • Sa is the arithmetic mean height
  • Sp is the maximum protrusion height
  • Ssk is the skewness
  • each field of view is The average value of 80 visual fields excluding the upper and lower 5 visual fields from the value is defined as the arithmetic mean height, maximum protrusion height, and skewness, respectively.
  • ISO parameter analysis conditions > ISO parameter analysis processing is performed under the following conditions.
  • ⁇ S-Filter Automatic/Normal probability paper Number of divisions: 300 Upper limit of calculation range: 3.000 Lower limit of calculation range: -3.000 - Parameters: Select "Height Parameters" - Output: Select "Parameter List”.
  • the film thickness is determined by measuring the thickness at five arbitrary locations using a dial gauge in accordance with JIS K7130 (1992) A-2 method, with 10 films stacked one on top of the other. The average value is divided by 10 to determine the film thickness.
  • the thickness of each layer was determined by the following method. A cross section of the film is cut out using a microtome in a direction parallel to the film width direction. The cross section is observed with a scanning electron microscope at a magnification of 5000 times, and the thickness ratio of each laminated layer is determined. The thickness of each layer is calculated from the obtained lamination ratio and the film thickness described above.
  • a copolymer consisting of methacrylic acid, methyl methacrylate, ethyl acrylate, and butyl methacrylate as a thermoplastic resin, and trimethylolpropane triacrylate and polyethylene glycol (number average molecular weight 600) dimethacrylate as photosensitive materials.
  • a mixture consisting of benzophenone and dimethylaminobenzophenone as photopolymerization initiators, hydroquinone as a stabilizer, and methyl violet as a coloring agent is used.
  • SEM scanning electron microscope
  • Fine wiring resist shape evaluation Regarding the 30 resist wiring patterns observed in the previous section (i), calculate the number of wiring patterns in which there is a missing part of 0.5 ⁇ m or more in the linear shape on the long side of the upper surface of the wiring pattern. Confirm and evaluate the fine wiring resist shape of the film as follows.
  • D The number of chips is 11 or more. In terms of fine wiring resist shape evaluation, A to C are good, and A is the best among them.
  • Fine wiring pinhole defect Regarding the 30 resist wiring patterns observed in the previous section (i), calculate the number of wiring patterns that have a missing part of 0.5 ⁇ m or more in the linear shape on the long side of the top surface of the wiring pattern. After checking, the film is evaluated for fine wiring pinhole defects as follows. A: The number of pinholes is 0. B: The number of pinholes is 1 or more and 5 or less. C: The number of pinholes with pinhole defects is 6 or more and 10 or less. D: The number of pinhole defects exceeds 10. In terms of fine wiring pinhole defect evaluation, A to C are good, and A is the best among them.
  • an addition reaction silicone resin (trade name: LTC750A, manufactured by Toray Dow Corning Silicone Co., Ltd.) and 2 parts by weight of a platinum catalyst (trade name: SRX212, manufactured by Toray Dow Corning Silicone Co., Ltd.) were added.
  • a coating liquid adjusted to have a solid content of 5% by weight is applied by gravure coating so that the coating thickness after drying is 0.1 ⁇ m, dried and cured at 120° C. for 30 seconds, and then wound up to obtain a release film.
  • a ceramic slurry 100 parts by weight of barium titanate (product name: HPBT-1, manufactured by Fuji Titanium Industries, Ltd.), 10 parts by weight of polyvinyl butyral (product name: BL-1, manufactured by Sekisui Chemical Co., Ltd.), and 5 parts by weight of dibutyl phthalate. Glass beads with a number average particle size of 2 mm are added to 60 parts by weight of toluene-ethanol (weight ratio 30:30), mixed and dispersed in a jet mill for 20 hours, and then filtered to prepare a paste. The obtained ceramic slurry is applied onto a release film using a die coater so that the thickness after drying is 2 ⁇ m, dried, and wound up to obtain a green sheet.
  • barium titanate product name: HPBT-1, manufactured by Fuji Titanium Industries, Ltd.
  • polyvinyl butyral product name: BL-1, manufactured by Sekisui Chemical Co., Ltd.
  • dibutyl phthalate 5 parts by weight of dibutyl phthal
  • a weight with a load of 1 kg is placed on top of the metal sample plate, and the metal sample plate is placed in close contact with the surface A of the sample or the surface B opposite to the surface A in the thickness direction by leaving it for 20 seconds.
  • the maximum value of the load (N; in newton units) detected when the attached thread is pulled under the following conditions is measured. Measurements were performed seven times, and the average value of the five measured values, excluding the top one and one bottom score, was taken as the slipperiness of the sample with respect to the metal sample plate, and evaluated as follows. AA to C are good, and AA is the best among them.
  • Static friction coefficient is less than 1.0
  • the laminated polyester film for dry film resist of the present invention was cut out into 11 mm x 0.75 mm (8.25 mm 2 ), and after focusing on the surface of the film P2 layer using an optical microscope (ECLIPSE LV100 manufactured by Nikon). , While shifting the focus to the inside of the film in the film thickness direction, an area from the film surface to 3 ⁇ m in the film thickness direction was observed. Measure the number of pieces.
  • the major axis here refers to the longest major axis dimension of a rectangular parallelepiped circumscribing the projected view of the coarse object in an image of the coarse object obtained when the film is vertically observed from the P2 layer side.
  • Lamination processing conditions Lamination conveyance speed: 2m/min
  • Lamination roll temperature 100°C
  • Lamination pressure 0.5MPa
  • the suitability for lamination at 100°C is evaluated by visually checking an A4 size laminated sample of a copper foil substrate and a biaxially oriented polyester film sample when the laminating roll temperature is 100°C.
  • 100°C laminate void evaluation (1) a. and b.
  • a to C are good, and A is the best among them.
  • (2) 100°C lamination wrinkle evaluation Visually inspect 10 A4 size laminate samples of copper foil substrates and biaxially oriented polyester samples laminated at 100°C using the laminating roll temperature used in the previous section (1). The presence or absence of wrinkles with a length of 1 cm or more was confirmed and evaluated as follows.
  • melt-polymerized PET substantially free of particles.
  • the resulting melt-polymerized PET had a glass transition temperature of 81°C, a melting point of 255°C, and an intrinsic viscosity of 0.62.
  • melt-polymerized PET substantially free of particles.
  • the resulting melt-polymerized PET had a glass transition temperature of 81°C, a melting point of 255°C, and an intrinsic viscosity of 0.50.
  • melt-polymerized PET substantially free of particles.
  • the resulting melt-polymerized PET had a glass transition temperature of 81°C, a melting point of 255°C, and an intrinsic viscosity of 0.40.
  • melt-polymerized PET substantially free of particles.
  • the resulting melt-polymerized PET had a glass transition temperature of 81°C, a melting point of 255°C, and an intrinsic viscosity of 0.80.
  • ⁇ Manufacture of MB-C> During the polymerization of PET-1, a cross-linked polystyrene particle slurry (cross-linked polystyrene-1) with a particle size of 300 nm dispersed in water at a particle concentration of 20% was added so that the amount added to PET was 1% by mass, and the PET base was Particle master pellets MB-C were obtained.
  • PET-1 master pellet MB-A (contains silica-1), master pellet MB-B (contains silica-2), master pellet MB-C (contains crosslinked polystyrene-1), master pellet MB-D (crosslinked polystyrene-1)
  • master pellet MB-A contains silica-1
  • master pellet MB-B contains silica-2
  • master pellet MB-C contains crosslinked polystyrene-1
  • master pellet MB-D crosslinked polystyrene-1
  • the amount of PET-1 and each master pellet added was the same as the amount of layers P1 to P3 listed in Table 1, and extrusion was carried out using each of the three extruders.
  • the treated unstretched film was sequentially stretched 3.5 times in the longitudinal direction and 4.0 times in the width direction using a biaxial stretching machine, for a total of 14.0 times, and then heat-treated at 230° C. under a constant length. Thereafter, relaxation treatment was performed in the width direction to obtain a biaxially oriented polyester film with a thickness of 16 ⁇ m.
  • Table 4 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 4, the surface properties of Surface A could be made good, and the film was good in all of slipperiness, uniformity of resist shape, green sheet shape, high temperature lamination property, and toughness.
  • Example 2 A biaxially oriented polyester film was obtained in the same manner as in Example 1, except that the plasma treatment conditions were changed as shown in Table 1.
  • Table 4 shows the properties of the obtained biaxially oriented polyester film.
  • the biaxially oriented polyester film obtained in Example 2 was able to have better surface properties on surface A, although the amount of water vapor in the plasma treatment atmosphere was lower than in Example 1.
  • the film had good properties in terms of slipperiness, uniformity of resist shape, green sheet shape, high-temperature lamination properties, and toughness.
  • the biaxially oriented polyester films obtained in Examples 3 and 4 had a lower plasma treatment intensity than in Example 1, so although the number of valley regions and peak regions and the average cross-sectional area were smaller, The film had sufficiently good properties in terms of uniformity, resist shape, uniformity of green sheet shape, high temperature lamination property, and toughness.
  • Example 5 A biaxially oriented film was obtained in the same manner as in Example 1, except that the resin constituting the P1 layer had the composition shown in Table 1.
  • Table 4 shows the properties of the obtained biaxially oriented polyester film.
  • the biaxially oriented polyester film obtained in Example 5 had a larger kurtosis on the surface A than in Example 1 due to the addition of alumina particles to the layer constituting the surface A, and the resist Although the resist evaluation of shape and pinhole defects was slightly inferior to that of Example 1, the film had sufficiently good slip properties, resist shape, uniformity of green sheet shape, high-temperature lamination properties, and toughness.
  • Example 6 In addition, in the biaxially oriented polyester film obtained in Example 6, the kurtosis of the surface A was larger than that of Example 1 due to the addition of silica particles to the layer constituting the surface A, and the resist shape and pinhole defects were reduced. Although the resist evaluation was slightly inferior to that of Example 1, the film had sufficiently good slip properties, resist shape, uniformity of green sheet shape, high temperature lamination properties, and toughness.
  • Example 7 A biaxially oriented film was obtained in the same manner as in Example 1, except that the resin constituting the P2 layer had the composition shown in Tables 1 and 2. The properties of the obtained biaxially oriented polyester film are shown in Tables 4 and 5.
  • the biaxially oriented polyester film obtained in Example 7 has an arithmetic mean height of surface B, a maximum protrusion height of Now, the skewness Ssk-B becomes smaller, and L/S of resist shape evaluation is 4/4 ⁇ m.
  • the film was better than Example 1 in the evaluation based on the wiring pattern. Furthermore, the film had sufficiently good slip properties, uniformity of green sheet shape, high-temperature lamination properties, and toughness.
  • the biaxially oriented polyester films obtained in Examples 8 and 9 had arithmetic average Although the height, maximum protrusion height, and skewness Ssk-B are smaller, and the slipperiness is inferior to Example 7, the slipperiness, resist shape, uniformity of green sheet shape, high-temperature lamination property, and toughness are all sufficient. It was a good film.
  • Example 10 A biaxially oriented film was obtained in the same manner as in Example 8, except that the resin constituting the P1 layer had the composition shown in Table 2. Table 5 shows the properties of the obtained biaxially oriented polyester film.
  • the intrinsic viscosity of the resin constituting surface A was made smaller than in Example 8, so that the trough and peak regions of surface A were The number of films and the average cross-sectional area were increased, and the slipperiness between the films was better than that of Example 8. Furthermore, the film had sufficiently good slip properties, uniformity of resist shape, green sheet shape, high temperature lamination properties, and toughness.
  • Example 11 12 A biaxially oriented film was obtained in the same manner as in Example 10, except that the plasma treatment conditions for Surface A were as shown in Table 2. Table 5 shows the properties of the obtained biaxially oriented polyester film.
  • the biaxially oriented polyester film obtained in Example 11 had a lower number of trough areas, peak areas, and average cross-sectional area on surface A than Example 10 due to the reduced plasma treatment intensity.
  • the film had a better uniformity of resist shape than Example 10.
  • the film had sufficiently good slip properties, uniformity of green sheet shape, high temperature lamination properties, and toughness.
  • the biaxially oriented polyester film obtained in Example 12 had lower plasma treatment strength than Example 11, so that the trough and peak areas of surface A were lower than in Example 11. Although the number of particles and the average cross-sectional area are reduced, and the slipperiness is inferior to that of Example 10, the film has sufficiently good slipperiness, resist shape, uniformity of green sheet shape, high-temperature lamination properties, and toughness. there were.
  • Example 13 A biaxially oriented film was obtained in the same manner as in Example 11, except that the resin constituting the P1 layer had the composition shown in Table 2. Table 5 shows the properties of the obtained biaxially oriented polyester film.
  • the biaxially oriented polyester film obtained in Example 13 had a lower average cross-sectional area of the valley region of surface A than Example 11 because the intrinsic viscosity of the resin was lower than that of Example 11. increased, and although the uniformity of resist shape was inferior to that of Example 11, the film had sufficiently good slip properties, uniformity of resist shape, green sheet shape, high-temperature lamination properties, and toughness. .
  • Example 14 A biaxially oriented film was obtained in the same manner as in Example 11, except that the resin extrusion filter constituting the P1 layer was used as shown in Table 2. Table 5 shows the properties of the obtained biaxially oriented polyester film.
  • the biaxially oriented polyester film obtained in Example 14 has an increased number of coarse particles with a major axis of 2.0 ⁇ m or more than in Example 11, and the resist shape is more uniform than in Example 11.
  • the film had sufficiently good slip properties, resist shape, uniformity of green sheet shape, high-temperature lamination properties, and toughness.
  • Example 15 A biaxially oriented film was obtained in the same manner as in Example 11, except that the stretching and relaxing conditions in the width direction were as shown in Table 2.
  • Table 5 shows the properties of the obtained biaxially oriented polyester film.
  • the biaxially oriented polyester film obtained in Example 15 had a higher dimensional change rate in the stretching direction when the film temperature was changed from 90°C in the width direction to 130°C than in Example 11. Although the film was larger and its high-temperature lamination properties were inferior to those of Example 11, the film had sufficiently good slip properties, resist shape, uniformity of green sheet shape, high-temperature lamination properties, and toughness.
  • Example 1 A biaxially oriented polyester film was obtained under the same conditions as in Example 1 except that no plasma treatment was performed.
  • Table 6 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 6, the biaxially oriented polyester film obtained in Comparative Example 1 has a small number of trough areas and peak areas on surface A, and a small average cross-sectional area, and has a low slipperiness with metal plates and slippage between films. It was a film of inferior quality.
  • Example 2 A biaxially oriented polyester film was obtained under the same conditions as in Example 1 except that the plasma treatment was performed in a nitrogen atmosphere containing no water vapor.
  • Table 6 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 6, the biaxially oriented polyester film obtained in Comparative Example 2 had small valley areas, small number of peak areas, and average cross-sectional area on surface A, and was a film with poor sliding properties with metal plates. Ta.
  • Example 3 A biaxially oriented polyester film was obtained under the same conditions as in Example 1, except that the plasma treatment atmosphere was set to a temperature of 20° C./humidity of 23.5% RH and an amount of water vapor in the atmosphere was set to 4 g/m 3 .
  • Table 6 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 6, the biaxially oriented polyester film obtained in Comparative Example 3 had small valley areas, small number of peak areas, and average cross-sectional area on surface A, and was a film with poor sliding properties with metal. .
  • Example 4 A biaxially oriented polyester film was obtained under the same conditions as in Example 1, except that the plasma treatment was performed in a nitrogen atmosphere containing no water vapor and the heat setting temperature was 245°C.
  • Table 6 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 6, in the biaxially oriented polyester film obtained in Comparative Example 4, the number of valley areas and peak areas on surface A, and the average cross-sectional area exceeded the good range, and the resist shape was poor and the toughness was poor. It was also a low film.
  • Example 5 A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the resin constituting the P1 layer had the composition shown in the table and the plasma treatment was not performed.
  • Table 6 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 6, in the biaxially oriented film obtained in Comparative Example 5, the number of peak regions on surface A, the average cross-sectional area, and the kurtosis exceeded the good range, and the resist evaluation of resist shape and pinhole defects The film had poor sliding properties with the metal plate due to the small number of valley regions.
  • Example 6 A biaxially oriented polyester film was obtained in the same manner as in Example 1, except that the resin constituting the P1 layer had the composition shown in the table. Table 6 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 6, in the obtained biaxially oriented film, the number of valley regions on surface A is smaller than the good range, and the number of peak regions and the average cross-sectional area are less than the good range, so the metal The film had poor sliding properties between the plate and the film. Further, since the average cross-sectional area of the valley region exceeded a good range, the film had poor uniformity in resist evaluation.
  • Example 7 A biaxially oriented polyester film was obtained in the same manner as in Example 1, except that the resin constituting the P1 layer had the composition shown in the table.
  • Table 6 shows the properties of the obtained biaxially oriented polyester film. As shown in Table 6, the obtained biaxially oriented film is a film with poor slipperiness between the metal plate and the film because the number of valley areas, the number of peak areas, and the average cross-sectional area of the surface A are less than a good range. there were.

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  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film de polyester biorienté susceptible d'arriver tant à des propriétés de glissement par rapport à des rouleaux métalliques qu'à une uniformité de la forme fine de réserve de câblage. Le film de polyester biorienté est conçu de façon qu'au moins une surface soit une surface A qui satisfait à (1a) et à (2a) quand on l'observe au MFA avec un champ de vision de 5-μm-carré dans des conditions spécifiques. (1a) Le nombre de creux présentant une hauteur par rapport à un plan de référence de −2 nm ou moins est compris dans la plage de 100/5 μm□ à 500/5 μm□ limites comprises. (2a) L'aire moyenne en section transversale des creux présentant une hauteur, par rapport au plan de référence, de −2 nm ou moins, est comprise dans la plage de 2 000 nm2 à 8 000 nm2 limites comprises.
PCT/JP2023/012045 2022-03-29 2023-03-24 Film de polyester biorienté WO2023190265A1 (fr)

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JP2022-053886 2022-03-29
JP2022053886 2022-03-29

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WO2023190265A1 true WO2023190265A1 (fr) 2023-10-05

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TW (1) TW202346443A (fr)
WO (1) WO2023190265A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06182195A (ja) * 1992-12-24 1994-07-05 Ii C Kagaku Kk 大気圧グロ−放電プラズマ処理法
JPH08167146A (ja) * 1994-12-09 1996-06-25 Matsushita Electric Ind Co Ltd 磁気記録媒体の製造方法
US5916674A (en) * 1997-02-05 1999-06-29 Ford Motor Company Article having a removable protective film
JP2002099063A (ja) * 2000-09-21 2002-04-05 Konica Corp 写真用ポリエステル支持体の製造方法
JP2002541466A (ja) * 1999-04-13 2002-12-03 パテル，ゴードハンハイ プラズマによる滅菌をモニターするためのインジケータ
JP2003155364A (ja) * 2001-11-22 2003-05-27 Tamapori Kk 貼合用プラスチックフィルム
JP2006523157A (ja) * 2003-03-31 2006-10-12 エクスアテック、エル．エル．シー． ポリカーボネート基体のためのインク
JP2013087206A (ja) * 2011-10-19 2013-05-13 Toray Ind Inc 成型用ポリエステルフィルム
JP2018053198A (ja) * 2016-09-30 2018-04-05 ユニチカ株式会社 ポリエステルフィルム
JP2020037620A (ja) * 2018-09-03 2020-03-12 東レ株式会社 熱可塑性樹脂フィルム
JP2021006639A (ja) * 2018-01-24 2021-01-21 大日本印刷株式会社 ポリエステル樹脂組成物

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06182195A (ja) * 1992-12-24 1994-07-05 Ii C Kagaku Kk 大気圧グロ−放電プラズマ処理法
JPH08167146A (ja) * 1994-12-09 1996-06-25 Matsushita Electric Ind Co Ltd 磁気記録媒体の製造方法
US5916674A (en) * 1997-02-05 1999-06-29 Ford Motor Company Article having a removable protective film
JP2002541466A (ja) * 1999-04-13 2002-12-03 パテル，ゴードハンハイ プラズマによる滅菌をモニターするためのインジケータ
JP2002099063A (ja) * 2000-09-21 2002-04-05 Konica Corp 写真用ポリエステル支持体の製造方法
JP2003155364A (ja) * 2001-11-22 2003-05-27 Tamapori Kk 貼合用プラスチックフィルム
JP2006523157A (ja) * 2003-03-31 2006-10-12 エクスアテック、エル．エル．シー． ポリカーボネート基体のためのインク
JP2013087206A (ja) * 2011-10-19 2013-05-13 Toray Ind Inc 成型用ポリエステルフィルム
JP2018053198A (ja) * 2016-09-30 2018-04-05 ユニチカ株式会社 ポリエステルフィルム
JP2021006639A (ja) * 2018-01-24 2021-01-21 大日本印刷株式会社 ポリエステル樹脂組成物
JP2020037620A (ja) * 2018-09-03 2020-03-12 東レ株式会社 熱可塑性樹脂フィルム

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