WO2024057778A1 - Film de polyester multicouche pour résines photosensibles sèches - Google Patents

Film de polyester multicouche pour résines photosensibles sèches Download PDF

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Publication number
WO2024057778A1
WO2024057778A1 PCT/JP2023/028897 JP2023028897W WO2024057778A1 WO 2024057778 A1 WO2024057778 A1 WO 2024057778A1 JP 2023028897 W JP2023028897 W JP 2023028897W WO 2024057778 A1 WO2024057778 A1 WO 2024057778A1
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Prior art keywords
film
less
ssk
polyester film
laminated polyester
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PCT/JP2023/028897
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Definitions

  • the present invention relates to a laminated polyester film for dry film resist, the surface of which is 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. Further, particles contained in the film may form coarse aggregates, or foreign matter may be unintentionally mixed in during the film forming process, and these coarse matter may cause pinholes in the resist. For this reason, the ultraviolet light irradiated surface (non-resist coated surface) of the support film must not only be smoother than before, but also slippery against the process metal roll, and be free from the generation and contamination of coarse particles. It has been demanded.
  • the conditions for the lamination process for dry film resists depend on the thermal properties of the resist layer and the combination with the copper foil substrate used. Generally, a rubber roll heated to 90°C or higher is used to apply pressure and adhere, but in recent years 120 ⁇ 130°C Demand for processing at high temperatures down to °C is increasing. Generally, when polyester film is heated to a temperature higher than its glass transition temperature, the film shrinks due to heat, so there is a difference in the rate of thermal dimensional change in the width direction between the resist layer and the copper foil substrate during lamination. Due to poor adhesion, a phenomenon in which air bubbles are trapped (laminate voids) occurs, leading to defects in the subsequent photoresist process. Therefore, it is important to control the thermal dimensional change rate of the biaxially oriented polyester film during the heating process from 90°C to around 130°C (temperature raising process) in order to improve lamination processability.
  • 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 3 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.
  • foreign matter may be mixed in from the outside during the coating and drying steps, so there is a concern that coarse matter may be formed.
  • Patent Document 4 discloses a method of performing plasma surface treatment using atmospheric pressure glow discharge on a surface that ensures handling properties (resist-uncoated surface) to form fine protrusions using a method that does not rely on particles.
  • handling properties resist-uncoated surface
  • Patent Document 4 discloses a method of performing plasma surface treatment using atmospheric pressure glow discharge on a surface that ensures handling properties (resist-uncoated surface) to form fine protrusions using a method that does not rely on particles.
  • large-diameter particles are used to ensure handling properties, there is a problem that they become a scattering factor of ultraviolet light during resist curing.
  • An object of the present invention is to provide a laminated polyester film for dry film resist that has excellent resist properties and slipperiness against metal rolls, and has excellent suitability for high-temperature lamination processing.
  • the present invention has the following configuration. That is, [I] A laminated polyester film for a dry film resist, in which the skewness Ssk of the surfaces A and B satisfies Ssk-A>Ssk-B, and the surfaces A and B are composed of at least two or more layers satisfying the following.
  • the number of protrusions with a height of 10 nm or more and less than 20 nm from the reference plane of surface A is 3000 pieces/mm 2 or more and less than 14000 pieces/mm 2
  • Skewness Ssk-A is 1.0 or more and 4.0 or less
  • Skewness Ssk-B is -0.1 or more and 1.0 or less
  • (Ssk-A) - (Ssk-B) is 0.1 or more and 3.0 or less
  • [II] Skewness Ssk of surface A and surface B
  • the laminated polyester film for dry film resist of the present invention has excellent resist properties and slipperiness against metal rolls, and has excellent suitability for high-temperature lamination processing.
  • FIG. 1 It is a conceptual diagram showing surface A (P1 layer surface) measured with a scanning white interference microscope.
  • Two-layer configuration diagram of the laminated polyester film for dry film resist of the present invention Three-layer configuration diagram of the laminated polyester film for dry film resist of the present invention A configuration diagram of a laminate for dry film resist in which a photosensitive resin is laminated on surface B of the laminated polyester film for dry film resist of the present invention.
  • the "laminated 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 formed 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.
  • the polyester film in the laminated polyester film for dry film resist of the present invention is biaxially oriented, which improves the mechanical strength of the film, making it less prone to wrinkling and improving winding properties.
  • the application of uniform stretching stress during the stretching process makes it possible to make the surface smoothness uniform across the entire 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 embodiment of the laminated polyester film for dry film resist of the present invention is a film in which the skewness Ssk of the surface A and the surface B satisfies Ssk-A>Ssk-B, and the surface A and the surface B are at least two layers that satisfy the following.
  • This is a laminated polyester film consisting of the above.
  • sample in the case of a sample whose longitudinal direction is unknown, 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 was subjected to image processing using the surface analysis software VS-Viewer Version 10.0.3.0 built into the microscope under the following conditions to determine the skewness SsK and the number of protrusions of 10 nm or more and less than 20 nm. seek. (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.
  • ⁇ Skewness Ssk> Scanning white interference microscopy measurements of 90 fields of view were performed on surfaces A and B of the laminated polyester, and for each measurement image subjected to the above-mentioned image processing, the following analysis conditions and "Height Ssk obtained by selecting "Parameters” and outputting the obtained numerical value group to the parameter sheet field is determined as the skewness, and the average value of 80 fields of view excluding the upper and lower 5 fields from the value of each field of view is the skewness Ssk of the measurement surface And so.
  • the skewness Ssk of each surface is defined as Ssk-A and Ssk-B.
  • ISO parameter analysis processing is performed under the following conditions.
  • the height threshold of 10 nm (R50 nm, height Protrusions with a height of 10 nm or more and less than 20 nm can be calculated by subtracting the number of particles displayed on the "Particle Analysis” screen detected at a threshold value of 0.01 ⁇ m and dividing by the measurement area (113 ⁇ m x 113 ⁇ m). Find the number (pieces/mm 2 ).
  • Protrusion analysis processing is performed under the following conditions.
  • ⁇ Analysis type Sudden analysis ⁇ Image correction: None/Processing Height threshold: 0.01 ⁇ m and 0.02 ⁇ m Particle shaping: None Reference height: Zero plane (average plane) ⁇ Judgment target height/depth: -10000 ⁇ m ⁇ h ⁇ 10000 ⁇ m Longest diameter: -10000 ⁇ m ⁇ d ⁇ 10000 ⁇ m Volume: V ⁇ 0.0000 ⁇ m 3 Aspect ratio: r ⁇ 0.0000 Histogram: Number of divisions: 50.
  • the "zero plane (average plane)" in the reference height (height 0 nm) setting is the measured image (113 ⁇ m x 113 ⁇ m) obtained by observing the microscope image using the method described above and performing the image processing described above. , a plane with the "average height (Ave)" automatically determined from the following formula is used.
  • ⁇ lx Range length in the X direction in each measurement image that has undergone the above image processing.
  • ⁇ ly Range length in the Y direction in each measurement image that has undergone the above image processing.
  • the fact that the skewness Ssk of surfaces A and B satisfies Ssk-A>Ssk-B indicates that surface A has more peaks than surface B.
  • surface A is a surface responsible for slipperiness
  • surface B is a surface that ensures smoothness and is suitable for coating with a photocurable resin.
  • the number of protrusions with a height of 10 nm or more and less than 20 nm indicates that fine protrusions are densely formed on the surface of the laminated polyester film for dry film resist. Due to the dense formation of minute protrusions, even if the skewness Ssk-A of surface A is within the range described below, it is possible to ensure slipperiness by suppressing adhesion when it comes into contact with a film or metal roll. becomes.
  • the slipperiness may deteriorate particularly because it is not sufficient to suppress adhesion to the metal roll. If the number is 14,000 pieces/mm 2 or more, the uniformity of the shape of the molded resist may be impaired.
  • the number of protrusions with a height of 10 nm or more and less than 20 nm is preferably 4000 pieces/mm 2 or more and 12000 pieces/mm 2 or less, 5000 pieces/mm 2 or more and 11000 pieces/mm 2 or less, and 5500 pieces/mm 2 or more and 10000 pieces/mm. 2 or less is more preferable.
  • the method of forming fine protrusions on the surface A of the laminated polyester film of the present invention and making the number of protrusions with a height of 10 nm or more and less than 20 nm within the above range comprises forming the film surface with microparticles having an average primary particle diameter of 5 nm or more and 30 nm or less. It is preferable to include it in the P1 layer, and it is more preferable that the average primary particle size is 10 nm or more and 20 nm or less.
  • the fine particles used here may be either inorganic particles or organic particles, or two or more types of particles may be used in combination.
  • 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.
  • examples include organic particles containing acrylic resin, styrene resin, silicone resin, polyimide resin, etc., and core-shell type organic particles.
  • alumina ( ⁇ alumina, ⁇ alumina, ⁇ alumina, ⁇ alumina) particles can be suitably used.
  • the amount of microparticles contained in the P1 layer constituting the surface A is preferably 0.5% by mass or more and less than 2.0% by mass, and 0.7% by mass or more and 1.7% by mass based on the entire mass of the P1 layer. % or less is more preferable.
  • the amount of microparticles is less than 0.5% by mass, the number of protrusions with a height of 10 nm or more and less than 20 nm may not be sufficiently formed, and the slipperiness with the film or metal roll may be impaired.
  • the amount of microparticles is 2.0% by mass or more, aggregates of microparticles are likely to be formed, which may cause shape wobble or pinhole defects in the resist.
  • methods for achieving the number of protrusions with a height of 10 nm or more and less than 20 nm within the above range include methods such as nanoimprint, which uses a mold to transfer the shape to the surface, corona treatment by UV irradiation or arc discharge, and glow discharge.
  • methods such as nanoimprint, which uses a mold to transfer the shape to the surface, corona treatment by UV irradiation or arc discharge, and glow discharge.
  • Examples include surface treatment such as plasma treatment.
  • the skewness Ssk-A of the surface A of the laminated polyester film for dry film resist of the present invention indicates the distribution (number, height, length) of peaks (protrusions) on the surface A.
  • the skewness Ssk-A increases or decreases depending on the particle size and content of the largest particle among the particles contained in the P1 layer.
  • the skewness Ssk-A is 1.0 or more and 4.0 or less. When the skewness Ssk-A is less than 1.0, the distribution of the peaks on the surface A is small, so that the slipperiness with the film or metal roll may be impaired.
  • skewness Ssk-A is greater than 4.0, particles contained in the P1 layer may scatter ultraviolet light during resist curing, causing wobble in the resist shape. Furthermore, when the laminate coated with a photosensitive resin is wound up into a roll, there is a possibility that the photosensitive resin will be dented due to the protrusions on the surface A pushing up. In addition, when a laminate coated with a photosensitive resin is wound up into a roll and stored, a large amount of air gets trapped inside the roll, and the oxygen and water vapor contained in the air are absorbed into the dry film resist laminate. It may penetrate through polyester films and protective films and deteriorate photosensitive resins.
  • the skewness Ssk-A of the surface A of the laminated polyester film for dry film resist of the present invention is preferably 1.2 or more and 3.0 or less, more preferably 1.5 or more and 2.5 or less.
  • the average primary particle size of the particles having the largest average primary particle size among the particles contained in the P1 layer constituting the surface A is 50 nm or more and 250 nm or less, and 100 nm or more. More preferably, the thickness is 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 P1 layer is less than 50 nm, the skewness Ssk-A may be less than 1.0, which may cause slippage with the film or metal roll. There are concerns that sexuality may be impaired.
  • the content of particles having the largest average primary particle size among the particles contained in the P1 layer which will be described later as having the largest average primary particle size of more than 250 nm among the particles contained in the P1 layer. Even if the thickness of the P1 layer is adjusted, the skewness Ssk-A may become larger than 4.0. There is a concern that sexual performance may decline.
  • the average primary particle diameter here refers to that determined under the following conditions. A cross section of the film is observed using a transmission electron microscope (TEM) at a magnification of 10,000 times. 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.
  • TEM transmission electron microscope
  • 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
  • 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.
  • 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 H-7100FA Measurement 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 P1 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 P1 layer is 0.003% by mass or more and 0.100% by mass based on the entire weight of the P1 layer in order to achieve both resist properties and slipperiness. % or less, more preferably 0.005% by mass or more and 0.030% by mass or less, and even 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 P1 layer is less than 0.005% by mass, sufficient peaks will not be formed on the surface and the skewness Ssk-A will be 1.0. If it is less than that, there is a possibility that the slipperiness with the film or metal roll will be impaired. If the content is more than 0.030% by mass, the skewness Ssk-A may be greater than 4.0, and the particles contained in the P1 layer scatter ultraviolet light during resist curing, causing the resist shape to change. Shakiness may occur.
  • the laminated polyester film for dry film resist of the present invention needs to have a skewness Ssk-B of the surface B of -0.1 or more and 1.0 or less.
  • a skewness Ssk-B of -0.1 or more and 1.0 or less indicates that the surface B is extremely smooth or has slight protrusions, and is suitable as a layer for laminating photosensitive resin for dry film resist applications. It can be used for. If the skewness Ssk-B is less than -0.1, the resist shape may deteriorate due to an increase in valleys, and if the skewness Ssk-B is greater than 1.0, the protrusions on the surface B may cause photosensitivity. There is a concern that unevenness may be transferred to the resin or that the resist shape may become loose.
  • the skewness Ssk-B of the surface B is preferably 0 or more and 0.7 or less, more preferably 0 or more and 0.5 or less.
  • the P2 layer constituting the surface B may substantially not contain particles, or the particles may be contained within the average primary particle diameter and content range described below. An example of this is letting people know.
  • the particles contained in the P2 layer may be either inorganic particles or organic particles.
  • inorganic particles include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, mica, alumina ( ⁇ alumina, ⁇ alumina, ⁇ alumina, ⁇ alumina). ) Mica, titanium mica, zeolite, talc, clay, kaolin, lithium fluoride, calcium fluoride, montmorillonite, zirconia, wet silica, dry silica, colloidal silica, etc. Examples include organic particles containing acrylic resin, styrene resin, silicone resin, polyimide resin, etc., and core-shell type organic particles.
  • the average primary particle diameter of the particles contained in the P2 layer is preferably 100 nm or less, more preferably 70 nm or less.
  • the skewness Ssk-B becomes larger than 1.0, which may cause unevenness to be transferred to the photosensitive resin or wobble in the resist shape.
  • the content of particles contained in the P2 layer is preferably 0.7% by mass or less, and preferably 0.3% by mass or less, based on the mass of the entire P2 layer. If the content of particles contained in the P2 layer is more than 0.7% by mass, the skewness Ssk-B of surface B may become larger than 1.0, and when a photosensitive resin is laminated on surface B. There is a possibility that unevenness may be transferred to the photosensitive resin or that the formed resist shape may become loose.
  • methods for forming protrusions in a range where the skewness Ssk-B is 1.0 or less include methods such as nanoimprinting, in which the shape is transferred to the surface using a mold, UV irradiation, Examples of surface treatments include corona treatment using arc discharge and plasma treatment using glow discharge.
  • UV irradiation, corona treatment using arc discharge, and plasma treatment using atmospheric pressure glow discharge are preferred, as they provide uniformity of treatment and cause less damage to the film. More preferred is plasma treatment using atmospheric pressure glow discharge. Atmospheric pressure here is in the range of 700 Torr to 780 Torr.
  • the film to be treated is introduced between opposing electrodes and an earth 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 and generate a glow discharge between the electrodes. This causes the film surface to be finely ashed, forming protrusions.
  • 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 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 may be damaged or ashing will progress, which is not desirable. Protrusions may not be formed.
  • 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 lower.
  • 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 laminated polyester film for dry film resist of the present invention needs to have a skewness Ssk difference between surface A and surface B, (Ssk-A)-(Ssk-B), of 0.1 or more and 3.0 or less.
  • the difference in skewness Ssk between surfaces A and B indicates that the shape difference between surfaces A and B is small after controlling Ssk-A and Ssk-B as described above. If (Ssk-A)-(Ssk-B) is less than 0.1, the formation of protrusions on the surface A may be insufficient, and there is a concern that the slipperiness with the film or metal roll may be impaired.
  • (Ssk-A) - (Ssk-B) is larger than 3.0, the difference in shape between surface A and surface B is large, so when the film is wound up after film formation and stored as a roll, surface A There is a possibility that unevenness is transferred to the surface B due to the pushing up of the protrusions, and that the unevenness is also transferred to the photosensitive resin after coating with the photosensitive resin, or that the resist shape becomes loose.
  • the skewness Ssk difference between surface A and surface B, (Ssk-A)-(Ssk-B), is preferably 0.3 or more and 2.0 or less, more preferably 0.5 or more and 1.5 or less.
  • the laminated polyester film for dry film resist of the present invention includes a P1 layer including a surface A, and a P2 layer including a surface B facing the P1 layer, and the P1 layer and the P2 layer are arranged on the outermost surface. It is preferable to have the above configuration.
  • the layer structure of the laminated polyester film of the present invention is preferably a P1 layer/P2 layer, or a structure including a P3 layer as an intermediate layer between the P1 layer and the P2 layer.
  • the P3 layer is preferably a layer that does not substantially contain particles.
  • 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.
  • IV (dl/g) when the intrinsic viscosity (IV) of the entire film is defined as IV (dl/g), IV (dl/g) is preferably 0.55 or more and 0.80 or less. preferable.
  • IV (dl/g) By setting the IV (dl/g) to 0.55 or more, the mechanical properties in the stretching film forming process can be improved and the reduction in film forming yield due to film tearing can be suppressed, and by setting the IV to 0.8 or less, , it is possible to suppress extrusion defects in the melt extrusion process.
  • the thickness of the P1 layer included in the surface A is preferably 0.05 ⁇ m or more and 0.4 ⁇ m or less. If the thickness of the P1 layer is less than 0.05 ⁇ m, the contained particles may easily detach, or the particles inside the P1 layer may not form enough protrusions, resulting in loss of slipperiness with the film or metal roll. There are concerns that If the thickness of the P1 layer is greater than 0.4 ⁇ m, the total number of particles included in the P1 layer increases, which may cause wobble in the resist shape.
  • the thickness of the P1 layer included in the surface A 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 maximum protrusion height of the surface A from the reference plane is 20 nm or more and 140 nm or less. If the maximum protrusion height is less than 20 nm, there is a concern that slipperiness with the film or metal roll may be impaired. If the maximum protrusion height is larger than 140 nm, ultraviolet light will be scattered by the protrusions on surface A, causing wobbling in the resist shape, or when the photosensitive resin coated laminate is rolled up and stored.
  • the maximum protrusion height on the surface A is more preferably 20 nm or more and 100 nm or less, further preferably 30 nm or more and 90 nm or less, and most preferably 40 nm or more and 80 nm or less.
  • the number of coarse particles with a major diameter of 2.0 ⁇ m or more existing in an area 3 ⁇ m in the film thickness direction from the P1 layer side as observed by an optical microscope is NP1 (pieces/8.25 mm 2 ), it is preferable that the number of NP1 is 20 or less.
  • 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 P1 layer side.
  • the number NP1 (pieces/8.25 mm 2 ) 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 is in the P1 layer, or up to the intermediate layer P3 layer if the P1 layer thickness is less than 3 ⁇ m.
  • This value reflects the number of aggregated particles contained in the NP1, and by setting NP1 to 10 particles/8.25 mm2 or less, pinhole defects can be prevented even in the next generation fine resist wiring (L/S 5/5 ⁇ m). It can be suppressed.
  • the preferable range of NP1 (pieces/8.25 mm 2 ) is 10 or less, more preferably 8 or less.
  • a method in which the preferable range is NP1 (pieces/8.25 mm 2 ), which is the number of coarse particles with a major axis of 2.0 ⁇ m or more existing in a region of 3 ⁇ m in the film thickness direction from the P1 layer side, is to use a polymer melted and extruded with an extruder.
  • This is a method of filtering the water using a filter. Particles contained in the laminated 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 filter that can capture 95% or more of foreign matter of 5 ⁇ m or larger.
  • particle master pellets are used to incorporate particles into the laminated polyester film of the present invention, it is more preferable to use a similar filter when creating 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 to be higher than the intrinsic viscosity of the particle master pellet, the number of coarse particles with a major axis of 2.0 ⁇ m or more existing in the above-mentioned 3 ⁇ m region in the film thickness direction can be reduced. can do.
  • 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 when containing the particles of the laminated polyester film for dry film resist of the present invention is as follows: For particles with the largest particle diameter among the particles added to the P1 layer, the particle content is the same as that of the particle master pellet. It is preferably 0.5% by mass or less, more preferably 0.3% by mass or less based on the weight of. If the particle content of the particle master pellet, which is the particle with the largest particle size among the particles added to the P1 layer, is greater than 0.5% by mass, it is added to and dispersed in a polyester resin that does not substantially contain particles during film formation. In this case, 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 may increase due to particle aggregation.
  • the particle content of the particle master pellet used when containing the particles of the laminated polyester film for dry film resist of the present invention is such that the particle content of the fine particles added to the P1 layer is 2.0% relative to the weight of the particle master pellet. It is preferably at most 1.5% by mass, more preferably at most 1.5% by mass. If the particle content of the particle master pellet of microparticles added to the P1 layer is larger than 2.0% by mass, the above-mentioned problems may occur due to agglomeration of particles when added to and dispersed in a polyester resin that does not substantially contain particles during film formation. In some cases, the number of coarse particles having a major axis of 2.0 ⁇ m or more existing in a region of 3 ⁇ m in the thickness direction of the film increases.
  • the laminated polyester film for dry film resist of the present invention has a film dimension change rate of ⁇ L90-130°C (ppm/°C) when the film temperature is raised from 90°C to 130°C, in the width direction (TD direction). ), and at least one direction in the longitudinal direction (MD direction) needs to be -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
  • the lower limit of ⁇ L90-130°C is more preferably 0 or more, and still more preferably 20 or more. Furthermore, by setting the ⁇ L90-130°C (ppm/°C) to 150 or less, 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 85 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.
  • corrugated iron wrinkles refers to a state in which the film has a wrinkled shape with a height of 5 mm or more in the width direction, similar to the shape of a corrugated sheet (corrugated iron sheet) used as a construction material.
  • 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.
  • the lower limit is more preferably 1.5% or more
  • 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. It is more preferable to set the direction in which the width direction is the width direction (TD direction) of the roll during lamination processing.
  • the thickness of the laminated polyester film for dry film resist of the present invention is preferably 11 ⁇ m or more and 50 ⁇ m or less, more preferably 12 ⁇ m or more and 30 ⁇ m or less.
  • optical properties such as light transmittance of the film can be further improved.
  • thickness By setting the thickness to 11 ⁇ m or more, flatness can be further improved when heat is applied during the process of using the film for various purposes.
  • a method for producing a laminated polyester film for dry film resist according to the present invention will be explained.
  • a method for obtaining the polyester resin used in the present invention a conventional polymerization method can be employed.
  • 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.
  • 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 laminated polyester film in the present invention can be obtained by a conventionally known manufacturing method, but by manufacturing the stretching and heat treatment steps under the above-mentioned conditions, the film size when raising the film temperature from 90°C to 130°C
  • the rate of change can be made into a desirable physical property as described above in at least one direction.
  • the method for manufacturing the laminated polyester film in the present invention includes, for example, heating and melting a dried raw material in an extruder as needed, extruding it from a die onto a cooled cast drum, and processing it into a sheet (melt casting method).
  • a drying casting method can be mentioned.
  • 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 that time, it is preferable to control the surface temperature of the film surface to be surface-treated so that it does not 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 laminated polyester film of the present invention without stretching tearing.
  • stretching in the longitudinal direction is performed by placing the unstretched film on a group of rolls heated to 70°C or higher. It is preferable to guide the film, stretch it in the longitudinal direction (vertical direction, ie, the direction in which the film travels), and cool it with a group of rolls set at a temperature of 20° C. or higher and 50° C. or lower. There is no particular restriction on the lower limit of the heating roll temperature during stretching in the longitudinal direction as long as it does not impair the stretchability of the sheet, but it is preferably higher than the glass transition temperature of the polyester resin used.
  • the preferable range of the stretching ratio in the longitudinal direction is 3.0 times or more and 4.8 times or less.
  • a more preferable range is 3.5 times or more and 4.8 times or less.
  • the stretching ratio in the longitudinal direction is 3.0 times or more, oriented crystallization progresses and film strength can be improved.
  • the stretching ratio is 4.8 times or less, the dimensional change rate ⁇ L90-130°C (ppm/ C) can be controlled within a preferable range, and at the same time, it is possible to suppress frequent breakage of the film during production due to excessive orientation and a decrease in productivity.
  • the resulting uniaxially stretched film stretched in the longitudinal direction is guided into a tenter while gripping both ends with clips, and is stretched in a direction perpendicular to the longitudinal direction (width direction) in an atmosphere heated to a temperature of 70°C to 160°C. ) is preferably stretched 3 times or more and 5 times or less.
  • Tmeta minute endothermic peak
  • DSC differential scanning calorimeter
  • the heat treatment temperature is preferably at least (melting point -40) °C and at most the melting point of the thermoplastic resin used, more preferably at least (melting point -40) °C and at most (melting point -15) °C.
  • 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 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 stretching ratio is 3 times or more and 4.8 times or less in both the longitudinal direction and the width direction, but the area ratio (longitudinal stretching ratio x width direction stretching ratio) is preferably 9 times or more and 22 times or less. , more preferably 9 times or more and 20 times or less.
  • 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.
  • a photosensitive resin is preferably laminated on the surface B side.
  • a film in which the skewness Ssk of surfaces A and B satisfies Ssk-A>Ssk-B this indicates that surface A is a surface that ensures handling properties, and surface B is a surface that ensures smoothness.
  • the method of laminating the photosensitive resin on the laminated polyester film for dry film resist of the present invention is not particularly limited, but a photosensitive resin composition prepared by mixing a photosensitive resin with an organic solvent to a predetermined concentration is coated.
  • An example of this method is to dry the organic solvent by drying the organic solvent.
  • the organic solvent include acetone, methyl ethyl ketone, methanol, ethanol, isopropyl alcohol, toluene, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and the like. These may be used alone or in combination of two or more.
  • a coating solution containing a mixture of photosensitive resin compositions is uniformly coated on one side of a carrier film by a method such as a roll coater method or a bar coater method, and then the coating solution is coated uniformly on one side of a carrier film using a method such as a roll coater method or a bar coater method.
  • a photosensitive resin layer can be laminated on the laminated polyester film for dry film resist.
  • the photosensitive resin when laminating a photosensitive resin, the photosensitive resin is coated on the surface B to ensure smoothness, and when dry film resist processing is performed, the surface A is exposed to ultraviolet light. It is preferable to do this in order to obtain a high-quality resist.
  • a film in which the skewness Ssk of surfaces A and B satisfies Ssk-A>Ssk-B as a dry film resist support by exposing the film to ultraviolet light from the side with a large skewness, the ultraviolet light caused by the particles contained in the layer can be removed. The effects of light refraction and scattering on the resist shape can be suppressed, and a high-quality resist shape can be obtained.
  • sample in the case of a sample whose longitudinal direction is unknown, 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 the 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 was subjected to image processing using the surface analysis software VS-Viewer Version 10.0.3.0 built into the microscope under the following conditions to determine the skewness SsK and the number of protrusions of 10 nm or more and less than 20 nm. , find the maximum protrusion height.
  • ⁇ Filter processing Median (3 x 3 pixels)
  • ⁇ Surface correction 4th order.
  • Skewness Ssk Scanning white interference microscopy measurements of 90 fields of view were performed on surfaces A and B of the laminated polyester, and for each measurement image subjected to the above-mentioned image processing, the following analysis conditions and "Height Ssk obtained by selecting "Parameters” and outputting the obtained numerical value group to the parameter sheet field is determined as the skewness, and the average value of 80 fields of view excluding the upper and lower 5 fields from the value of each field of view is the skewness Ssk of the measurement surface And so.
  • the skewness Ssk of each surface is defined as Ssk-A and Ssk-B.
  • the same operation was performed on all 90 fields of view that were measured, and the average value of the 80 fields of view excluding the field of view where the maximum value and the minimum value of each field of view were 5 measurement values was calculated as the height of the A side of the sample.
  • ⁇ Particle analysis conditions Protrusion analysis processing is performed under the following conditions.
  • ⁇ Analysis type Sudden analysis
  • ⁇ Image correction None/Processing Height threshold: 0.01 ⁇ m and 0.02 ⁇ m
  • Particle shaping None Reference height (surface): Zero surface (average surface)
  • ⁇ Judgment target height/depth -10000 ⁇ m ⁇ h ⁇ 10000 ⁇ m
  • Longest diameter -10000 ⁇ m ⁇ d ⁇ 10000 ⁇ m
  • Volume V ⁇ 0.0000 ⁇ m 3
  • the "zero plane (average plane)" in the reference height (height 0 nm) setting is the measured image (113 ⁇ m x 113 ⁇ m) obtained by observing the microscope image using the method described above and performing the image processing described above. , a plane with the "average height (Ave)" automatically determined from the following formula is used.
  • ⁇ lx Range length in the X direction in each measurement image that has undergone the above image processing
  • ⁇ ly Range length in the Y direction in each measurement image that has undergone the above image processing
  • ⁇ h(x, y) As described above Height at each image point (x, y) in the measurement image that has undergone image processing.
  • ⁇ 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.
  • each layer of the film 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.
  • 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).
  • TEM Transmission electron microscope
  • 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).
  • 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 number average particle diameter of each particle.
  • Particle content concentration 1 g of a sample obtained by scraping off only the P1 layer, P2 layer, and P3 layer portions of the laminated polyester film for dry film resist of the present invention was poured into 200 ml of 1N-KOH methanol solution, heated to reflux, and the polymer dissolve. 200 ml of water was added to the solution after dissolution, and the liquid was then centrifuged to sediment the particles, and the supernatant liquid was removed. The particles were further washed with water and centrifuged twice. The particles thus obtained were dried and their mass (g) was measured to calculate the concentration (% by mass) of the particles contained in each layer of the laminated polyester film for dry film resist.
  • the contained particles include organic particles
  • select a solvent that dissolves the polymer but not the organic particles dissolves the polymer without overheating and refluxing, centrifuges the particles, and determines the particle content (mass%) in each layer. ) was calculated.
  • Whether the contained particles are organic particles or inorganic particles can be confirmed by the presence or absence of detection of inorganic substances when the particles are observed using a generally known method such as SEM-EDX.
  • the measurement was performed using the following method. (1-1) Dissolve the measurement sample in 100 mL of orthochlorophenol to create a solution with a concentration higher than 1.2 g/100 mL.
  • the weight of the measurement sample subjected to orthochlorophenol is defined as the measurement sample weight.
  • the laminated polyester film for dry film resist of the present invention was cut out into a size of 11 mm x 0.75 mm (8.25 mm 2 ), and after focusing on the surface of the film P1 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 P1 layer side.
  • TMA/SS6000 thermomechanical measuring device
  • TMA/SS6100 Thermomechanical analysis (TMA) measurement> Measurement is performed using a thermomechanical measuring device TMA/SS6000 (manufactured by Seiko Instruments Inc.) and the attached analysis software TMA/SS6100 (manufactured by Seiko Instruments Inc.) in the following manner.
  • a laminated polyester film for dry film resist is cut into strips of 30 mm in the measurement direction and 4 mm in the direction orthogonal to the measurement direction, and attached to the device so that the distance between the chucks is 20 mm in the measurement direction.
  • the thermal dimensional change rate ⁇ L (ppm/°C) of the laminated polyester film for dry film resist is determined from the dimensions at each film temperature, that is, the distance between the chucks, when heated using a temperature increase program that is then held for 10 minutes.
  • the film temperature refers to the cell temperature (Temp Cel) recorded every 20 seconds during measurement using the included analysis software TMA/SS6100 (manufactured by Seiko Instruments Inc.), and the distance between the chucks is It refers to the TMA length (TMA ⁇ m) recorded during measurement using the attached analysis software TMA/SS6100 (manufactured by Seiko Instruments Inc.).
  • thermal dimensional change rate ⁇ L in the process of increasing temperature from 90°C to 130°C 90-130°C is determined from the film dimensions at film temperatures of 90°C and 130°C using the following equation (1). The measurement was carried out twice and the average value was taken as the thermal dimensional change rate ⁇ L90-130°C (ppm/°C) in the process of increasing the temperature from 90°C to 130°C, which the laminated polyester film for dry film resist has.
  • ⁇ L90-130°C (ppm/°C) [(Film dimension at 130°C ( ⁇ m)) - (Film dimension at 90°C ( ⁇ m))]/[130°C-90°C] x 10000... (1 )
  • the width direction and longitudinal direction of the laminated polyester film for dry film resist are measured to determine the ⁇ L90-130°C (ppm/°C) in the width direction and longitudinal direction.
  • 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 pinhole defect Regarding the 30 resist wiring patterns observed in the previous section (1), calculate the number of wiring patterns that have a missing part of 0.5 ⁇ m or more in 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.
  • the resist layer surface of the laminated polyester film sample for dry film resist provided with the obtained resist layer was stacked so that it was in contact with a metal substrate (copper foil substrate) laminated with a 3 ⁇ m thick copper foil cut into A4 size. After that, lamination is performed under the following conditions using a laminator equipped with a temperature-controllable rubber pressure roller.
  • 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 laminated polyester film sample for dry film resist when the laminating roll temperature is 100°C.
  • 100°C laminate void evaluation (1) a. and b. 10 A4 size laminate samples of copper foil substrates and laminated polyester film samples for dry film resist that were laminated at a laminating roll temperature of 100°C obtained in Section 1 were visually inspected for lamination voids (lifting of the laminate layer). The presence or absence of voids was confirmed, and the following evaluation was performed based on the number of samples in which the major axis of voids exceeded 1 mm. A: Laminate voids occur in one or less of the 10 laminated samples.
  • B Out of 10 laminated samples, laminate voids occur in 2 or more and 3 or less.
  • C Out of 10 laminated samples, laminate voids occur in 4 or more and 6 or less.
  • D Lamination voids occur in 7 or more of the 10 laminate samples. As for the 100°C laminate void evaluation, A to C are good, and A is the best among them.
  • 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.
  • alumina particles (alumina-1) with an average primary particle diameter of 20 nm dispersed in ethylene glycol were mixed with 95% foreign matter of 5 ⁇ m or more so that the amount added to PET was 2% by mass. After high-precision filtration using the above-described filter, the particles were added to obtain particle master pellets MB-A. The intrinsic viscosity of the obtained particle master pellet MB-A was 0.59.
  • a crosslinked polystyrene particle slurry (crosslinked polystyrene-1) with a particle size of 300 nm dispersed in water at a particle concentration of 20% is mixed with foreign substances of 5 ⁇ m or more so that the amount added to PET is 1% by mass. It was added after high-precision filtration with a filter that captures 95% or more to obtain PET-based particle master pellets MB-D. The intrinsic viscosity of the obtained particle master pellet MB-D was 0.59.
  • ⁇ Manufacture of MB-E> During the polymerization of PET-1, a slurry of crosslinked polystyrene particles (crosslinked polystyrene-2) with a particle size of 140 nm dispersed in water at a particle concentration of 20% was added to a slurry of crosslinked polystyrene particles of 5 ⁇ m or more so that the amount added to PET was 0.2% by mass. After high-precision filtration with a filter that captures 95% or more of foreign substances, it was added to obtain PET-based particle master pellets MB-D. The intrinsic viscosity of the obtained particle master pellet MB-E was 0.59.
  • Example 1 After drying PET-1, master pellet MB-A (containing alumina), master pellet MB-B (containing silica-1), and master pellet MB-C (containing silica-2) under reduced pressure at 180°C for 2 and a half hours, PET -1 and each master pellet are blended so that the amount of particles contained in each master pellet is the amount of P1 layer to P3 layer listed in Table 1, supplied to each of the three extruders, melt-extruded, and filtered with a filter. After that, the P1 layer/P3 layer/P2 layer were combined in a feed block so as to be laminated, and then wound through a T-die onto a cooling roll kept at 42°C using an electrostatic casting method, and cooled and solidified.
  • P1 layer/P3 layer/P2 layer were combined in a feed block so as to be laminated, and then wound through a T-die onto a cooling roll kept at 42°C using an electrostatic casting method, and cooled and solidified.
  • An unstretched film was obtained.
  • a high-precision filter that captures 95% or more of foreign matter of 5 ⁇ m or more is used for filter filtration of the P1 layer and P2 layer, and a high precision filter that captures 95% of foreign matter of 2 ⁇ m or more is used for filter filtration of the P3 layer.
  • Melt extrusion is performed using a high-precision filter that collects the above.
  • This unstretched film was guided between the opposing electrode and the ground roll, and nitrogen gas was introduced into the device, and the atmospheric pressure was set such that the E value was 220 W min/m 2 with respect to the surface on the P2 layer side (surface B). Glow discharge treatment was performed. Further, at that time, the earth roll was cooled so that the film surface temperature on the treated surface was 30°C.
  • the treated unstretched film is passed through a static elimination roll whose roll temperature is set to 25° C., it is sequentially biaxially stretched under the conditions listed in Table 1.
  • the film was introduced into a group of stretching rolls heated to 60°C to 100°C in the longitudinal direction, and stretched to a total of 3.8 times by a stretching operation, and then transferred to a tenter, where it was stretched by 4.3 times in the width direction.
  • a laminated polyester film having a thickness of 16 ⁇ m was obtained by heat treating at 230° C. under a fixed length and relaxing treatment in the width direction as shown in Table 1.
  • Tables 1 and 2 The structure and properties of the obtained laminated polyester film are shown in Tables 1 and 2.
  • the film had good dry film resist suitability, high temperature lamination suitability, storage suitability, and handling suitability.
  • Table 1 shows the particles contained in PET-1, master pellet MB-A (contains alumina), master pellet MB-B (contains silica-1), and master pellet MB-D (contains crosslinked polystyrene-1) in the P1 layer.
  • a laminated polyester film was obtained in the same manner as in Example 1, except that the contents were as shown in Table 1 and the particles contained in the master pellet MB-A (containing alumina) of the P2 layer were as shown in Table 1. The structure and properties of the obtained laminated polyester film are shown in Tables 1 and 2.
  • Example 7 A laminated polyester film was obtained in the same manner as in Example 1, except that the resin composition of the P2 layer was as shown in Table 1, and the surface of the P2 layer side was not subjected to plasma treatment.
  • the structure and properties of the obtained laminated polyester film are shown in Tables 1 and 2.
  • Example 9 A laminated polyester film was obtained in the same manner as in Example 1 except that the resin composition in the P2 layer was as shown in Table 3-1. The structure and properties of the obtained laminated polyester film are shown in Tables 3-1 and 4-1.
  • Example 11 12 A laminated polyester film was obtained in the same manner as in Example 1, except that the thicknesses of the P1 layer, P2 layer, and P3 layer were as shown in Table 3-1. The structure and properties of the obtained laminated polyester film are shown in Tables 3-1 and 4-1.
  • Example 13 and 14 Instead of using master pellet MB-B (containing silica-1) as the resin constituting the P1 layer, it is contained in master pellet MB-C (containing silica-2) or master pellet MB-D (containing crosslinked polystyrene-1).
  • master pellet MB-B containing silica-1
  • master pellet MB-C containing silica-2
  • master pellet MB-D containing crosslinked polystyrene-1).
  • a laminated polyester film was obtained in the same manner as in Example 1, except that the particles were used in the amounts shown in Table 3. The structure and properties of the obtained laminated polyester film are shown in Tables 3-1 and 4-1.
  • Example 15 A laminated polyester film was obtained in the same manner as in Example 1, except that the filter used when melt-extruding the resin constituting the P1 layer was as shown in Table 3-2. The structure and properties of the obtained laminated polyester film are shown in Tables 3-2 and 4-2.
  • Example 16 17 A laminated polyester film was obtained in the same manner as in Example 1, except that the sequential biaxial stretching conditions of the laminated polyester film were the heat treatment temperature, relaxation temperature, and relaxation ratio listed in Table 3-2.
  • the structure and properties of the obtained laminated polyester film are shown in Tables 3-2 and 4-2. As shown in Table 4-2, although the suitability for high-temperature lamination processing was inferior to that of Example 1, the film had no practical problems.
  • Example 18, 19 Instead of using master pellet MB-B (containing silica-1) as the resin constituting the P1 layer, the particles contained in master pellet MB-E (containing crosslinked polystyrene-2) as shown in Table 3-2 were used.
  • a laminated polyester film was obtained in the same manner as in Example 1 except that the amount was used. The structure and properties of the obtained laminated polyester film are shown in Tables 3-2 and 4-2.
  • Example 6 As shown in Table 6, the film was significantly inferior to Example 1 in either dry film resist suitability or handling suitability.
  • Example 3 A laminated polyester film was obtained in the same manner as in Example 1, except that the particles contained in the master pellet MB-B (containing silica-1) in the P1 layer were adjusted to the content shown in Table 5. The structure and properties of the obtained laminated polyester film are shown in Tables 5 and 6.
  • Example 6 As shown in Table 6, the film was significantly inferior to Example 1 in either dry film resist suitability or handling suitability.
  • Example 5 A laminated polyester film was obtained in the same manner as in Example 1, except that the resin composition in the P2 layer was as shown in Table 5, and the surface on the P2 layer side was not subjected to plasma treatment. The structure and properties of the obtained laminated polyester film are shown in Tables 5 and 6.
  • Example 6 As shown in Table 6, the film was significantly inferior in handling suitability compared to Example 1.
  • Example 6 A laminated polyester film was obtained in the same manner as in Example 1 except that the resin composition in the P2 layer was as shown in Table 5. The structure and properties of the obtained laminated polyester film are shown in Tables 5 and 6.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème abordé par la présente invention consiste à fournir un film de polyester multicouche pour des résines photosensibles sèches, le film de polyester multicouche présentant une excellente aptitude à la stratification à températures élevées, tout en ayant d'excellentes caractéristiques de résine photosensible et d'excellentes propriétés de glissement par rapport à un rouleau métallique. À cet effet, l'invention concerne un film de polyester multicouche pour résines photosensibles sèches, le film de polyester multicouche étant composé d'au moins deux couches, l'asymétrie Ssk d'une surface A et l'asymétrie Ssk d'une surface B satisfaisant Ssk-A > Ssk-B, et la surface A et la surface B satisfaisant les exigences décrites ci-dessous. (1) Le nombre de saillies qui ont une hauteur qui n'est pas inférieure à 10 nm mais inférieure à 20 nm à partir de la surface de référence de la surface A est supérieur à 3 000 par mm2 mais inférieur à 14 000 par mm2. (2) L'asymétrie Ssk-A est comprise entre 1,0 et 4,0. (3) L'asymétrie Ssk-B est comprise entre -0,1 et 1,0. (4) ((Ssk-A) - (Ssk-B)) est compris entre 0,1 et 3,0.
PCT/JP2023/028897 2022-09-15 2023-08-08 Film de polyester multicouche pour résines photosensibles sèches WO2024057778A1 (fr)

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JP2022-146753 2022-09-15

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021001284A (ja) * 2019-06-24 2021-01-07 東レ株式会社 二軸配向ポリエステルフィルムおよびその製造方法
WO2021172455A1 (fr) * 2020-02-27 2021-09-02 富士フイルム株式会社 Film de transfert, et procédé de fabrication de stratifié
JP2022061012A (ja) * 2020-10-05 2022-04-15 東レ株式会社 工程フィルム、樹脂組成物膜の積層体、樹脂組成物膜、樹脂粗製物膜の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021001284A (ja) * 2019-06-24 2021-01-07 東レ株式会社 二軸配向ポリエステルフィルムおよびその製造方法
WO2021172455A1 (fr) * 2020-02-27 2021-09-02 富士フイルム株式会社 Film de transfert, et procédé de fabrication de stratifié
JP2022061012A (ja) * 2020-10-05 2022-04-15 東レ株式会社 工程フィルム、樹脂組成物膜の積層体、樹脂組成物膜、樹脂粗製物膜の製造方法

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