WO2024029384A1 - ドライフィルムレジスト支持体用二軸配向ポリエステルフィルム - Google Patents

ドライフィルムレジスト支持体用二軸配向ポリエステルフィルム Download PDF

Info

Publication number
WO2024029384A1
WO2024029384A1 PCT/JP2023/026984 JP2023026984W WO2024029384A1 WO 2024029384 A1 WO2024029384 A1 WO 2024029384A1 JP 2023026984 W JP2023026984 W JP 2023026984W WO 2024029384 A1 WO2024029384 A1 WO 2024029384A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
layer
less
biaxially oriented
oriented polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/026984
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
敏弘 千代
卓司 東大路
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP2023547192A priority Critical patent/JPWO2024029384A1/ja
Priority to KR1020247035520A priority patent/KR20250048175A/ko
Priority to CN202380055747.4A priority patent/CN119604400A/zh
Publication of WO2024029384A1 publication Critical patent/WO2024029384A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material

Definitions

  • the present invention improves high-temperature lamination processability in the dry film resist processing process by controlling the rate of thermal dimensional change at a specific temperature, and provides a second dry film resist support with excellent resist optical properties and film productivity. It relates to an axially oriented polyester film.
  • polyester resin Due to its good processability, polyester resin is used in various industrial fields. In addition, products processed into film from these polyester resins (biaxially oriented polyester films) play an important role in today's life, including industrial applications, optical product applications, packaging applications, and magnetic recording tape applications.
  • a transparent film is used as a support, and a photocurable resin layer (resist layer) is provided on the surface, and a substrate (copper foil substrate) is laminated with a thin copper film.
  • a dry film resist method is used, in which the wiring shape is drawn using photoresist technology for each film, and the copper wiring is formed by cleaning after peeling off the film. It becomes necessary to perform very fine processing of 5 ⁇ m.
  • a biaxially oriented polyester film is wound up into a roll after being formed in a manufacturing process.
  • the films will adhere to each other, resulting in poor film winding properties. Therefore, a method is known in which the film surface is roughened to a certain extent (forming protrusions on the film surface) by adding/containing particles to the film in order to ensure the windability of the film.
  • the film surface is roughened to a certain extent (forming protrusions on the film surface) by adding/containing particles to the film in order to ensure the windability of the film.
  • the conditions for the lamination process for dry film resists vary depending on the thermal properties of the resist layer and the combination with the copper foil substrate used, and generally a rubber roll heated to 90°C or higher is used to apply pressure and adhere, but in recent years Demand for processing at high temperatures of up to 130°C is increasing.
  • 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.
  • Patent Documents 1 to 3 As a method for controlling thermal dimensional changes in a biaxially oriented polyester film, techniques for controlling dimensional changes before and after heat treatment by performing high temperature heat treatment in the film forming process are described in Patent Documents 1 to 3. A technique for similarly controlling thermal dimensional changes by using a heat-resistant polyester resin is described in Patent Document 4.
  • Patent Documents 1 and 2 the heat treatment temperature and the temperature of the relaxation treatment necessary to control the dimensional change rate are low, making it difficult to control the thermal dimensional change rate at the target temperature of 90°C to 130°C. be.
  • control of the thermal dimensional change rate is achieved in a 4.5 ⁇ m thin film by combining high-area double stretching and re-stretching.
  • the film lacks rigidity (firmness), and it is easy to wrinkle due to the slight shaking of the roll during lamination processing.Furthermore, when tension is applied to the film to eliminate wrinkles, film tears occur, so lamination is difficult. Processing suitability is significantly reduced.
  • Patent Document 4 heat-resistant polyester resin is used as a copolymerization component, so while it is possible to control thermal properties, the copolymerization component increases surface roughness and causes unevenness in optical properties within the film. This is not preferable because the optical properties are significantly deteriorated when the film is used as a dry film resist support film.
  • An object of the present invention is to provide a biaxially oriented polyester film for a dry film resist support that has excellent suitability for high-temperature lamination, as well as excellent resist optical properties and film productivity.
  • the biaxially oriented polyester film for a dry film resist support according to [I] or [II].
  • N 10 nm 600
  • the dry film resist according to [X] which has a particle concentration lower than that of the P1 layer or a layer containing no particles (P3 layer) between the P1 layer and the P2 layer. Biaxially oriented polyester film for support.
  • N P1 the number of coarse particles with a major diameter of 2.0 ⁇ m or more existing in a region 3 ⁇ m in the film thickness direction from the P1 layer side observed by an optical microscope is N P1 (pieces/8.25 mm), then N P1 is 20 or less, the biaxially oriented polyester film for a dry film resist support according to [VII].
  • the present invention is a biaxially oriented polyester film for a dry film resist support, which has excellent suitability for high-temperature lamination processing, and excellent resist optical properties and film productivity.
  • FIG. 2 is a conceptual diagram showing a surface of a protrusion (P2 layer surface) measured with a scanning white interference microscope.
  • Two-layer configuration diagram of the biaxially oriented polyester film of the present invention Three-layer configuration diagram of the biaxially oriented polyester film of the present invention
  • the present invention relates to biaxially oriented polyester films.
  • the film dimensional change rate is ⁇ L 90-130°C (ppm/°C) when the film temperature is raised from 90°C to 130°C
  • a biaxially oriented polyester film for a dry film resist support which is -50 or more and 150 or less in at least one direction, and has a total film thickness T ( ⁇ m) of 11 or more and 50 or less.
  • the biaxially oriented polyester film for a dry film resist support of the present invention preferably has a structure containing a polyester resin as a main component.
  • the biaxially oriented polyester film referred to in the present invention refers to a film whose main component is polyester resin.
  • 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.
  • the dicarboxylic acid components constituting this polyester include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and 1,8-naphthalene.
  • Examples include aromatic dicarboxylic acids such as dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, and 4,4'-diphenyl ether dicarboxylic acid, or ester derivatives thereof.
  • the diol constituents constituting this polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol.
  • examples include aliphatic diols such as cyclohexanedimethanol, alicyclic diols such as spiroglycol, and those in which a plurality of the above-mentioned diols are connected.
  • polyester resins used in the present invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalene dicarboxylate (PEN), and dicarbonate of PET.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene-2,6-naphthalene dicarboxylate
  • dicarbonate of PET polyesters in which isophthalic acid or naphthalene dicarboxylic acid is copolymerized as part of the acid component, and polyesters in which cyclohexanedimethanol, spiroglycol, and diethylene glycol are copolymerized as part of the diol component of PET are preferably used, and among these, polyethylene terephthalate is particularly preferred. is preferred.
  • the biaxially oriented polyester film for dry film resist support of the present invention is biaxially oriented, which improves the mechanical strength of the film, makes it less likely to wrinkle, and improves winding properties. Further, by applying uniform stretching stress in the stretching process, the surface smoothness can be made uniform throughout the film.
  • the term "biaxial orientation" as used herein refers to one that exhibits a biaxial orientation pattern in wide-angle X-ray diffraction. Polyester films 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 and relaxation treatment to complete crystal orientation. The details will be described later.
  • IV (dl/g) when the intrinsic viscosity (IV) of the entire film is defined as IV (dl/g), IV (dl/g) is 0.55 or more and 0.80 or less. It is preferable that By setting the IV (dl/g) to 0.55 or less, the mechanical properties in the stretching film forming process can be improved and reducing the yield of film forming 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 structure of the biaxially oriented polyester film for dry film resist support of the present invention includes a P1 layer/P2 layer provided with a running surface layer containing particles (P1 layer) and a layer having protrusions (P2 layer), which will be described later. It is preferable to have a laminated structure of at least two or more layers.
  • the P2 layer or the P4 layer containing particles within a range that does not affect the thermal dimensional change rate and optical properties of the present invention may be used as the underlayer of the P1 layer.
  • a four-layer stacked structure of P1 layer/P2 layer/P3 layer/P2 layer or P1 layer/P4 layer/P3 layer/P2 layer is also a preferable structure. The details will be described later.
  • the method of laminating the P1 layer, P2 layer, and P3 layer made of polyester resin is not particularly limited, but may include the coextrusion method described below, or feeding other resin layer materials into an extruder into the film during film formation.
  • a method in which the film is melt-extruded and laminated while being extruded from a die (melt lamination method), a method in which films after film formation are laminated via an adhesive layer, and a method in which the film is provided by coating during or after the film formation process. (in-line coating method, offline coating method), etc. can be used, and among them, a co-extrusion method that allows simultaneous formation of protrusions by the above-mentioned treatment and lamination is preferably used.
  • T is preferably 11 or more and 50 or less.
  • T ( ⁇ m) is preferably 11 or more and 50 or less.
  • the total film thickness T ( ⁇ m) is set to 50 or less, it is possible to suppress the occurrence of pinhole defects in resist wiring by causing light scattering in the photoresist due to foreign matter inside the film generated from polyester resin raw materials. Moreover, it is possible to prevent the film rigidity of the biaxially oriented polyester film from increasing excessively and to improve the processability.
  • the lower limit of the total film thickness T ( ⁇ m) is more preferably 15 or more.
  • the upper limit of the total film thickness T ( ⁇ m) is more preferably 35 or less, and even more preferably 25 or less.
  • the biaxially oriented polyester film for dry film resist support of the present invention has a film dimensional change rate of ⁇ L 90-130°C (ppm/°C) when the film temperature is raised from 90°C to 130°C. At least one of the width direction (TD direction) and longitudinal direction (MD direction) needs to be -50 or more and 150 or less.
  • the film dimensional change rate ⁇ L 90-130°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 for dry film resist support 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, If so, it is a value that indicates contraction.
  • TMA thermomechanical analysis
  • the lower limit of ⁇ L 90-130°C is more preferably 0 or more, and still more preferably 20 or more. Further, by setting the ⁇ L 90-130°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 ⁇ L 90-130°C (ppm/°C) is more preferably 85 or less.
  • heat treatment and relaxation in the width direction are carried out in the transverse stretching process when forming a biaxially stretched polyester film, which will be described later.
  • this can be achieved by subjecting the biaxially stretched film to heat treatment at a certain temperature or higher and also subjecting it to relaxation treatment at a certain temperature or higher.
  • the biaxially oriented 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. It is preferable to apply Improving thermal dimensional stability while maintaining flatness by slightly shrinking in the width direction while relieving excess orientation stress remaining in polyester resin molecular chains within a biaxially oriented film through biaxial stretching. can be achieved. By setting the ratio of relaxation treatment in the width direction to 1% or more, the effect of relieving the orientation stress can be obtained, and by setting the ratio of relaxation treatment in the width direction to 4% or less, the biaxially oriented polyester film due to rapid thermal shrinkage can be obtained.
  • 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 is performed. After this, it is preferable to perform a relaxation treatment in the width direction at a temperature of 90° C. or higher and 150° C. or lower, which corresponds to the laminating temperature range, at a rate of 0.5% or higher and 3% or lower. 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 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 0 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 .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. is most preferable.
  • 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 above ⁇ L 90-130°C (ppm/°C) is In a more preferable form, the direction in which the value is -50 or more and 150 or less is the width direction (TD direction) of the roll during lamination.
  • the biaxially oriented polyester film for dry film resist support of the present invention has a film temperature of 90°C to 130°C in the in-plane perpendicular direction to the direction in which ⁇ L 90-130°C (ppm/°C) is -50 to 150. It is preferable that the film dimensional change rate ⁇ L 90-130°C (ppm/°C) when the temperature is raised to 0°C is -200 or more and 0 or less.
  • ⁇ L 90-130°C (ppm/°C) in the in-plane perpendicular direction to the direction in which ⁇ L 90-130°C (ppm/°C) is -50 or more and 150 or less is -200 or more and 0 or less
  • Lamination processing is performed by setting ⁇ L 90-130°C (ppm/°C) in the in-plane perpendicular direction to the direction in which ⁇ L 90-130°C (ppm/°C) is -50 or more and 150 or less to be -200 or more and 0 or less.
  • the in-plane direction perpendicular to the above direction is the roll unwinding direction.
  • the lower limit of ⁇ L 90-130°C (ppm/°C) in the in-plane perpendicular direction to the direction in which ⁇ L 90-130°C (ppm/°C) is ⁇ 50 or more and 150 or less is more preferably ⁇ 150 or more.
  • the above-mentioned method As a method of controlling the film dimensional change rate ⁇ L 90-130°C (ppm/°C) in a preferable range when the film temperature is raised from 90°C to 130°C in the in-plane perpendicular direction to the above-mentioned direction, the above-mentioned method is used. This can be controlled by performing heat treatment/relaxation treatment and stretching in the longitudinal direction at a stretching ratio of 3.0 times or more and 4.8 times or less in the film forming process described later. A more preferable range is 3.5 times or more and 4.8 times or less.
  • the biaxially oriented polyester film for dry film resist support of the present invention can be used when the film temperature is raised from 90°C to 110°C in the direction where ⁇ L 90-130°C (ppm/°C) is -50 or more and 150 or less. It is preferable that the film dimensional change rate ⁇ L 90-110°C (ppm/°C) is 0 or more. By setting the above ⁇ L 90-110°C (ppm/°C) to 0 or more, when the film is laminated at a temperature of 90°C to 110°C, the film expands and the dimensional change rate with the resist layer is reduced.
  • a more preferable range of ⁇ L 90-110°C (ppm/°C) is 30 or more, and still more preferably 70 or more.
  • a more preferable range for the upper limit is 150 or less, and more preferably 120 or less, so that the biaxially oriented polyester film expands more than the resist layer during the lamination process, so that the copper foil substrate and the resist layer It is possible to suppress the occurrence of floating between the two.
  • the biaxially oriented polyester film for dry film resist support of the present invention has a film dimensional change rate of ⁇ L 110-130°C (ppm/°C) when the film temperature is raised from 110°C to 130°C in the above direction. It is preferable that it is 0 or more.
  • ⁇ L 110-130°C ppm/°C
  • the film expands and the dimensional change rate with respect to the resist layer is reduced. This is preferable because it can suppress the occurrence of a difference in . Further, this is preferable because it can assist in propagating the stress in the width direction during pressurization by the high-temperature processing roll.
  • the preferred range of ⁇ L 110-130°C is 10 or more, more preferably 20 or more.
  • a more preferable range for the upper limit is 250 or less, and more preferably 100 or less, so that the biaxially oriented polyester film expands significantly compared to the resist layer during the lamination process, and the bond between the copper foil substrate and the resist layer is reduced. It is possible to suppress the occurrence of floating in between.
  • the root mean square roughness Sq (nm) of at least one surface of the biaxially oriented polyester film for dry film resist support of the present invention is 0.8 or more and less than 3.0.
  • Root mean square roughness (Sq) is an average roughness value that estimates the effects of tall protrusions and deep valleys more than the arithmetic mean roughness (Sa), which is generally used as surface roughness. This is a value that reflects the amount of rough protrusions and dents that occur on the surface with a low probability, and is a useful value for estimating the resist optical properties and film runnability required for dry film resist support films.
  • the root mean square roughness is a value measured by the measurement method described below based on ISO 25178, which is determined by the software attached to the scanning white interference microscope by performing measurement with a scanning white interference microscope (VertScan) according to the method described below.
  • the root mean square roughness Sq (nm) of at least one surface is 0.8 or more and less than 3.0.
  • the side is the opposite side to the side on which the resist layer is provided, and is the side that is irradiated with ultraviolet light with a wavelength of 365 nm (hereinafter sometimes referred to as resist light), which is generally used for resist processing (hereinafter referred to as the running surface). (sometimes referred to as). If the root mean square roughness Sq (nm) is 0.8 or more, the friction between the film surface and the conveyance roll will increase and scratches will occur on the film surface in the film manufacturing process and dry film resist processing process.
  • the root mean square roughness Sq (nm) is more preferably 2.0 or more.
  • the upper limit of the root mean square roughness Sq (nm) is more preferably 2.9 or less.
  • both surfaces of the biaxially oriented polyester film for dry film resist support of the present invention satisfies 0.8 or more and less than 3.0, either surface may be used as the running surface. It is preferable to use a layer containing particles having a larger average primary particle diameter as the running surface from the viewpoint of suppressing the influence of light scattering of resist light by the contained particles from directly propagating to the resist layer.
  • the biaxially oriented polyester film for a dry film resist support of the present invention preferably has a layer (P1 layer) containing particles having an average primary particle diameter of 70 nm or more and 200 nm or less.
  • P1 layer containing particles having an average primary particle diameter of 70 nm or more and 200 nm or less.
  • a more preferable form of the biaxially oriented polyester film for dry film resist support of the present invention is that it has a layer (P1 layer) containing particles having an average primary particle diameter of 70 nm or more and 150 nm or less.
  • the P1 layer is disposed on the running surface side, which is the opposite surface to the surface on which the resist layer is provided.
  • the P1 layer does not contain particles having an average primary particle diameter of more than 200 nm.
  • the P1 layer includes particles with an average primary particle size of less than 70 nm, as well as particles with an average primary particle size of 70 nm or more and 200 nm or less. It may contain.
  • inorganic particles or organic particles may be used, or two or more types of particles may be used in combination.
  • Inorganic particles that can be used include, for example, calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, alumina ( ⁇ alumina, ⁇ alumina, ⁇ alumina, ⁇ alumina). ), mica, mica, titanium mica, zeolite, talc, clay, kaolin, lithium fluoride, calcium fluoride, montmorillonite, zirconia, silica (wet silica, dry silica, colloidal silica), etc.
  • organic particles include organic particles containing acrylic resin, styrene resin, silicone resin, polyimide resin, etc., and core-shell type organic particles.
  • alumina or silica is preferable from the viewpoint of matching the refractive index with the biaxially oriented polyester film and minimizing the effect on resist optical properties
  • styrene resin is preferable because biaxially oriented polyester is used for the same reason. It is preferable because its refractive index is close to that of the film.
  • T P1 ( ⁇ m) When the thickness of the P1 layer in the biaxially oriented polyester film for a dry film resist support of the present invention is defined as T P1 ( ⁇ m), it is preferable that T P1 ( ⁇ m) is 0.03 or more and 0.35 or less. By setting T P1 ( ⁇ m) to 0.35 or less, light scattering of resist light by particles contained in the P1 layer can be suppressed, pinhole defects during resist wiring formation can be suppressed, and T P1 ( ⁇ m) is 0.03 or more, it is possible to suppress particles contained in the P1 layer from falling off during film running. A more preferable range of the upper limit value of T P1 ( ⁇ m) is 0.30 or less, and most preferably 0.25 or less.
  • the root mean square roughness Sq P1 (nm) of the surface of the P1 layer in the biaxially oriented polyester film for a dry film resist support of the present invention is 0.8 or more and less than 3.0 depends on the particles in the layer. It is preferable to use the P1 layer, which can suppress light scattering of resist light, as a running surface.
  • the root mean square roughness Sq P1 (nm) of the P1 layer surface is 0.8 or more, surface scratches occur due to friction between the P1 layer surface and the conveyance roll in the film manufacturing process and dry film resist processing process. can be restrained from doing so.
  • the root mean square roughness Sq P1 (nm) of the surface of the P1 layer is less than 3.0, scattering of ultraviolet light for resist processing in the photoresist process on the film surface is suppressed, and the resist It is possible to suppress the occurrence of distortion in the wiring shape of the wiring.
  • the lower limit of the root mean square roughness Sq P1 (nm) of the surface of the P1 layer is more preferably 2.0 or more.
  • the upper limit of the root mean square roughness Sq P1 (nm) of the surface of the P1 layer is more preferably 2.9 or less.
  • the biaxially oriented polyester film for a dry film resist support of the present invention preferably has a P2 layer that satisfies the following (1) and (2) on the surface opposite to the P1 layer.
  • (1) Does not contain particles with an average primary particle diameter of 200 nm or more.
  • N 10 nm 600
  • the P2 layer of the present invention does not contain particles with an average primary particle size of 200 nm or more, so that sudden coarse protrusions are formed on the surface of the P2 layer, and a resist layer is formed on the surface of the P2 layer. At this time, it is possible to suppress the occurrence of resist layer defects due to the transfer of the uneven shape on the surface of the P2 layer. Also, from the viewpoint of suppressing light scattering of resist light, it is preferable not to contain particles having an average primary particle diameter of 200 nm or more.
  • the particles contained in the P2 layer preferably do not contain particles with an average primary particle size of 150 nm or more, and even more preferably do not contain particles with an average primary particle size of 100 nm or more. Most preferably, it does not contain particles with a diameter of 70 nm or more.
  • N 10 nm protrusions/mm 2
  • N10nm 600 or more and 12,000 or less
  • the runnability in the film forming process of the biaxially stretched film can be improved.
  • the biaxially oriented polyester film of the present invention is used as a film for dry film resist support
  • N10nm represents the number of fine protrusions formed on the surface of the P2 layer, and it affects the runnability of the P2 layer. This is a value that has an impact.
  • the biaxially oriented polyester film can be formed without using particles with an average primary particle diameter of 200 nm or more in the P2 layer. In the manufacturing process, it is possible to ensure running performance with the conveyance roll, and it is possible to suppress the occurrence of surface scratches.
  • the number of protrusions with a height of 10 nm or more (N 10 nm (protrusions/mm 2 ) to 12,000 or less, the interface between the P2 layer surface and the resist layer becomes rough and the resist light is scattered at the interface. It can be suppressed.
  • the lower limit of the number of protrusions with a height of 10 nm or more N 10 nm (pieces/mm 2 ) is more preferably 1000 or more, and the upper limit of the number of protrusions with a height of 10 nm or more N 10 nm (pieces/mm 2 ) is more preferably 1000 or more. More preferably, it is 10,000 or less.
  • particles having a specific particle diameter as described below are used.
  • a method in which a shape is transferred to the surface using a mold such as nanoimprinting, a method in which an unstretched sheet is subjected to plasma surface treatment using atmospheric pressure glow discharge, and then biaxial stretching is performed.
  • a method of performing biaxial stretching by plasma treatment using atmospheric pressure glow discharge or a method of incorporating minute particles described below is used. It is preferable.
  • Plasma surface treatment using atmospheric pressure glow discharge can be performed in the polyester film manufacturing process, whether the treatment is applied to the unstretched film after extrusion or to the stretched film.
  • atmospheric pressure plasma treatment it is most preferable to subject the unstretched film to plasma surface treatment using atmospheric pressure glow discharge. This is because the amorphous polyester portion is scraped off by plasma surface treatment using atmospheric pressure glow discharge, and the crystalline polyester portion remaining on the surface grows as convex portions in the subsequent stretching process, forming fine protrusions on the surface. It is.
  • the 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 processed (ashed) to form 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 strength (E value) determined by the method below is preferably in the range of 50 to 1000 W ⁇ min/m 2 from the viewpoint of protrusion formation, and more preferably in the range of 150 to 800 W ⁇ min/m 2 . be.
  • the discharge treatment strength (E value) is 50 W ⁇ min/m 2 or more, protrusions can be sufficiently formed, and when the discharge treatment strength (E value) is 1000 W ⁇ min/m 2 or less, it is possible to form a polyester film. Excessive damage can be suppressed and the generation of surface foreign matter can be reduced.
  • E value Vp ⁇ Ip/(S ⁇ Wt)
  • Vp Applied voltage
  • Ip Applied current
  • S Processing speed (m/min)
  • Wt processing width (m).
  • the soft amorphous portion is ashed first.
  • finer protrusions can be formed by performing atmospheric pressure glow discharge treatment, and the above N 10 nm can be increased.
  • the particles contained in the P2 layer either inorganic particles or organic particles may be used, or two or more types of particles may be used in combination, but as mentioned above, the particles contained in the P2 layer have an average primary diameter. is preferably less than 200 nm, more preferably contains particles less than 150 nm, even more preferably less than 100 nm, most preferably less than 70 nm.
  • Inorganic particles that can be used include, for example, calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, alumina ( ⁇ alumina, ⁇ alumina, ⁇ alumina, ⁇ alumina). ), mica, mica, titanium mica, zeolite, talc, clay, kaolin, lithium fluoride, calcium fluoride, montmorillonite, zirconia, silica (wet silica, dry silica, colloidal silica), etc.
  • organic particles include organic particles containing acrylic resin, styrene resin, silicone resin, polyimide resin, etc., and core-shell type organic particles.
  • alumina is preferred because it has a high Mohs hardness and is effective in suppressing scratches on the film surface
  • styrene resin is preferred because its refractive index is close to that of the biaxially oriented polyester film.
  • IV P2 (dl/g) when the intrinsic viscosity (IV) of the entire P2 layer is defined as IV P2 (dl/g), IV P2 (dl/g) should be 0.50 or more and 0.63 or less. is preferred. IV is a number that reflects the length of the molecular chain, and the shorter the molecular chain, the easier the polyester molecules will be oriented and crystallized during stretching and heat treatment. By doing so, when using the atmospheric pressure plasma treatment, formation of protrusions in the biaxial stretching film forming process can be promoted and runnability can be improved.
  • T P2 When the thickness of the P2 layer in the biaxially oriented polyester film of the present invention is T P2 ( ⁇ m), T P2 is preferably 0.2 or more and 2.0 or less.
  • T P2 ( ⁇ m) of the P2 layer By setting the thickness T P2 ( ⁇ m) of the P2 layer to 0.2 or more, when including particles in the P2 layer or controlling the intrinsic viscosity, the effect of forming protrusions by plasma treatment using atmospheric pressure glow discharge can be efficiently suppressed. Obtainable. Further, it is more preferable that the thickness T P2 ( ⁇ m) of the P2 layer is 2.0 or less from the viewpoint of suppressing deterioration of the optical properties of the entire film.
  • the upper limit of the thickness T P2 ( ⁇ m) of the P2 layer is more preferably 1.5 or less.
  • the P3 layer preferably has a lower particle concentration than the P1 layer or does not contain particles.
  • the amount of particles contained in the P3 layer as described above, it is possible to minimize the addition of raw materials that have been thermally degraded after undergoing melt extrusion, such as recovered raw materials for particle-containing master pellets and particle-containing films. This is preferable from the viewpoint of suppressing the generation of degraded products such as oligomers during high-temperature heat treatment.
  • the recovered raw material refers to the raw material that is made into pellets after crushing the polyester film that has been formed.
  • the P3 layer in the biaxially oriented polyester film has a lower concentration of particles than the P1 layer and has a lower concentration of particles with an average primary particle size of 70 nm or more and 200 nm or less than the P1 layer, or contains particles. A form without is more preferable.
  • the P3 layer should have an intrinsic viscosity (IV) of 0.55 or more, from the viewpoint of improving the mechanical properties of the entire polyester film. It is preferable to have a three-layer structure of P1 layer/P3 layer/P2 layer made of polyester resin.
  • the number of coarse particles with a major axis of 2.0 ⁇ m or more existing in a region 3 ⁇ m in the film thickness direction from the P1 layer side observed with an optical microscope is N P1 (pieces/8.25 mm 2 ). In this case, it is preferable that N P1 is 20 or less.
  • N P1 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 is N P1 (pieces/8.25 mm 2 ) is the P1 layer, and if the P1 layer thickness is less than 3 ⁇ m, the intermediate layer P3 layer This value reflects the number of agglomerated particles contained up to this point, and by setting N P1 to 10 particles/8.25 mm2 or less, pinhole defects can be avoided even in next-generation fine resist wiring (L/S 5/5 ⁇ m). The occurrence can be suppressed.
  • a preferable range of N P1 (pieces/8.25 mm 2 ) is 10 or less, more preferably 8 or less.
  • N P1 (pieces/8.25 mm 2 ), which is the number of coarse particles with a major diameter of 2.0 ⁇ m or more existing in an area of 3 ⁇ m in the film thickness direction from the P1 layer side, is a preferable range is to melt and extrude with an extruder.
  • This is a method of filtering the polymer 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, so the filter is 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.
  • 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 conventional polymerization method can be used to obtain the polyester film 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.
  • 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 of the present invention can be obtained by a conventionally known manufacturing method. Specifically, the polyester film of the present invention uses a method (melt casting method) in which dry raw materials are heated and melted in an extruder as needed, extruded from a die and extruded onto a cooled casting drum to form a sheet. can do. Another method is to dissolve the raw material in a solvent, extrude the solution from a die onto a support such as a cast drum or endless belt to form a film, and then dry and remove the solvent from the film layer to process it into a sheet. A method such as a solution casting method can also be used.
  • an extruder is used for each layer constituting the biaxially oriented polyester film, the raw materials for each layer are melted, and these are placed between the extrusion device and the die.
  • a method co-extrusion method is preferably used in which the materials are laminated in a molten state in a merging device provided, then introduced into a die, and extruded from the die onto a cast drum to form a sheet.
  • the laminated sheet is brought into close contact with static electricity on a cast drum cooled to a surface temperature of 20° C. or more and 60° C. or less, and is cooled and solidified to produce an unstretched film.
  • the surface temperature of the cast drum By setting the surface temperature of the cast drum to 20°C or higher, the crystalline polyester portion on the surface of the unstretched film can be further increased, and the effect of forming fine protrusions after stretching can be obtained by plasma surface treatment using atmospheric pressure glow discharge. I can do it. Furthermore, by setting the surface temperature of the cast drum to 60° C. or lower, it is possible to suppress the unstretched film from sticking to the cast drum, and to obtain an unstretched film with little thickness unevenness in the film running direction. A more preferable range of the surface temperature of the cast drum is 25°C or more and 55°C or less.
  • the unstretched film obtained here is subjected to surface treatment such as plasma surface treatment using atmospheric pressure glow discharge.
  • surface treatment such as plasma surface treatment using atmospheric pressure glow discharge.
  • These surface treatments may be performed immediately after obtaining the unstretched film or after stretching the film in the running direction (hereinafter sometimes referred to as the longitudinal direction), but in the present invention, surface treatment of the unstretched film is performed as described above. This is preferable from the viewpoint of further promoting the formation of protrusions.
  • 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).
  • 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 ⁇ L 90-130°C (ppm /°C) can be controlled within a preferable range, and it is also possible to suppress frequent breakage of the film during production due to excessive orientation, which reduces 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 conditions for the heat treatment and relaxation treatment are as described above to control the dimensional change rate ⁇ L 90-130°C (ppm/°C) in a preferable range when the temperature is increased from 90°C to 130°C in the above-mentioned direction.
  • 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.
  • 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 each measurement result is taken as the number of protrusions in 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 processed under the following conditions using the surface analysis software VS-Viewer Version 10.0.3.0 built into the microscope to calculate the root mean square roughness and each height. Find the number of protrusions.
  • Image processing is performed in the following order. ⁇ Interpolation processing: Complete interpolation ⁇ Filter processing: Median (3 x 3 pixels) ⁇ Surface correction: 4th order.
  • Root mean square roughness (Sq) Scanning white interference microscopy measurements were performed on the surface of biaxially oriented polyester for 90 fields of view, and for each measurement image subjected to the image processing described above, the following analysis conditions and "Height Parameters” were added to the "ISO parameters" analysis within the surface analysis software. Find the root mean square roughness Sq (nm) obtained by selecting "" and outputting the obtained numerical value group to the parameter sheet field, and calculate the average value of 90 fields of view as the root mean square roughness Sq (nm) of the measurement surface. shall be.
  • Sq P1 (nm) be the root mean square roughness of the surface of the P1 layer determined by the method described above
  • SqP2 (nm) be the root mean square roughness of the surface of the P2 layer.
  • ISO parameter analysis processing is performed under the following conditions.
  • Protrusion analysis processing is performed under the following conditions.
  • ⁇ Analysis type Sudden analysis ⁇ Image correction: None/Processing Height threshold: 0.01 ⁇ 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 (Reference height: zero plane (average plane)) 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 measured image subjected to image processing B. Thermal dimensional change rate ⁇ L (ppm/°C) (i) Thermomechanical analysis (TMA) measurement Measurement is performed in the following manner using a thermomechanical measuring device TMA/SS6000 (manufactured by Seiko Instruments Inc.) and the accompanying analysis software TMA/SS6100 (manufactured by Seiko Instruments Inc.). A biaxially oriented polyester film 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 apparatus so that the distance between the chucks is 20 mm in the measurement direction.
  • the thermal dimensional change rate ⁇ L (ppm/° C.) of the biaxially oriented polyester film is determined from the dimensions at each film temperature, that is, the distance between the chucks, when heated using a temperature raising 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 formula (1). The measurement is carried out twice and the average value is taken as the thermal dimensional change rate ⁇ L 90-130°C (ppm/°C) of the biaxially oriented polyester film in the process of increasing the temperature from 90°C to 130°C.
  • ⁇ L 90-130°C (ppm/°C) [(Film dimension at 130°C ( ⁇ m)) - (Film dimension at 90°C ( ⁇ m))] / [130°C-90°C] ⁇ 10000...
  • the width direction and longitudinal direction of the biaxially oriented polyester film are measured to determine ⁇ L 90-130° C. (ppm/° C.) in the width direction and longitudinal direction.
  • the width direction is defined as the direction in which the temperature (ppm/°C) satisfies -50 or more and 150 or less.
  • thermal dimensional change rate ⁇ L in the process of increasing temperature from 90°C to 110°C 90-110°C is determined from the film dimensions at film temperatures of 90°C and 110 °C using the following equation (2). The measurement was carried out twice and the average value was taken as the thermal dimensional change rate ⁇ L 90-110°C (ppm/°C) of the biaxially oriented polyester film in the process of increasing the temperature from 90°C to 110°C.
  • ⁇ L 90-130°C (ppm/°C) [(Film dimension at 110°C ( ⁇ m)) - (Film dimension at 90°C ( ⁇ m))] / [110°C-90°C] ⁇ 10000... ( 2)
  • the width direction of the biaxially oriented polyester film is measured and the widthwise ⁇ L 90-130°C (ppm/°C) is determined.
  • thermal dimensional change rate ⁇ L in the process of increasing temperature from 110°C to 130° C 110-130°C is determined from the film dimensions at film temperatures of 90°C and 110°C using the following equation (2). The measurement was carried out twice and the average value was taken as the thermal dimensional change rate ⁇ L 110-130°C (ppm/°C) of the biaxially oriented polyester film in the process of increasing the temperature from 110°C to 130°C.
  • ⁇ L 110-130°C (ppm/°C) [(Film dimension at 130°C ( ⁇ m)) - (Film dimension at 110°C ( ⁇ m))] / [130°C-110°C] ⁇ 10000... ( 2)
  • the width direction of the biaxially oriented polyester film is measured and the widthwise ⁇ L 90-130°C (ppm/°C) is determined.
  • Lamination thickness (T P1 , T P2 , T P3 )
  • a cross section of the biaxially oriented polyester film is cut out using a microtome in a direction parallel to the width direction of the film.
  • the cross section is observed with a scanning electron microscope at a magnification of 5,000 to 20,000 times, and the thickness ratio of each laminated layer is determined.
  • the thickness of each layer is calculated from the obtained lamination ratio and the total film thickness obtained in the above section (i).
  • ⁇ sp (solution viscosity/solvent viscosity)-1, K is Huggins constant (set to 0.343).)
  • 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.
  • Intrinsic viscosity (IV) of biaxially oriented polyester film The biaxially oriented polyester film of the present invention was measured in the same manner as in the previous section (i) to obtain the intrinsic viscosity (IV) of the biaxially oriented polyester film.
  • Measuring device Transmission electron microscope (TEM) Hitachi model H-7100FA Measuring conditions: Accelerating voltage 100kV Measurement magnification: 200,000 times to 800,000 times Sample preparation: Ultra thin film sectioning method (RuO4 staining).
  • the equivalent circle diameter was defined as the average primary particle peak diameter D 1 (nm).
  • D 1 the average primary particle peak diameter
  • the number-based particle size distribution has two or more peaks. In this case, each peak value is taken as the average primary particle diameter (peak diameter D 1 ) of each particle.
  • Particle content concentration 1 g of a sample obtained by scraping off only the P1 layer, P2 layer, and P3 layer of the biaxially oriented polyester film of the present invention was added to 200 ml of 1N-KOH methanol solution, and heated to reflux to dissolve the polymer. let After dissolution, 200 ml of water was added to the solution, 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 content concentration (% by mass) of the particles contained in each layer portion of the biaxially oriented polyester film.
  • 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.
  • Haze after heat treatment H1
  • the 5 cm square sample used in the previous section (i) is placed in an oven kept at 150° C., and an accelerated heat treatment test is performed for 1 hour. Thereafter, the film is taken out of the oven and cooled to room temperature, and then the film haze after heat treatment is measured in the same manner as in the previous section (i). The average of the measured values in three trials is defined as the haze (H1) of the biaxially oriented polyester film after heat treatment.
  • the biaxially oriented polyester film of the present invention was cut out to a size of 11 mm x 0.75 mm (8.25 mm 2 ), and the surface of the P1 layer was examined using an optical microscope (ECLIPSE LV100 manufactured by Nikon). After focusing, the area from the film surface to 3 ⁇ m in the film thickness direction was observed while shifting the focus to the inside of the film in the film thickness direction, and the major axis 2.
  • Count the number of coarse particles with a size of 0 ⁇ m or more. The number of measurements is n 3, and their average value is the number of coarse particles N P1 (pieces/8.25 mm 2 ) in the sample.
  • grades A to C are good, and A is the best among them.
  • a to C are good, and A is the best among them.
  • a photosensitive resin layer is applied on the surface of the P2 layer by gravure coating in a dark room so that the coating thickness is 15 ⁇ m.
  • a photosensitive resin layer 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.
  • Lamination processing conditions Lamination conveyance speed: 2m/min
  • the suitability for lamination processing at 100°C was determined by setting the laminating roll temperature to 120°C.
  • the suitability for lamination at 120° C. is evaluated by visually checking a laminated sample of a copper foil substrate and a biaxially oriented polyester sample.
  • Laminate voids occur in 1 or less of the 10 laminate samples.
  • B Lamination voids occur in 2 or more and 3 or less of the 10 laminate samples.
  • 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.
  • B Out of 10 laminate samples, laminate wrinkles occur in 2 or more and 3 or less.
  • C Out of 10 laminated samples, laminate wrinkles occur in 4 or more and 6 or less.
  • D Laminate wrinkles occur in 7 or more of the 10 laminated samples. In terms of 100°C lamination wrinkle evaluation, A to C are good, and A is the best among them.
  • Laminate voids occur in 1 or less of the 10 laminate 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 120°C laminate void evaluation, A to C are good, and A is the best among them.
  • B Out of 10 laminate samples, laminate wrinkles occur in 2 or more and 3 or less.
  • C Out of 10 laminated samples, laminate wrinkles occur in 4 or more and 6 or less.
  • D Laminate wrinkles occur in 7 or more of the 10 laminated samples. As for 120°C lamination wrinkle evaluation, A to C are good, and A is the best among them.
  • i-line ultraviolet ray having a peak wavelength of 365 nm
  • the photosensitive resin layer is placed in a container containing developer N-A5 and developed for about 1 minute. Thereafter, it is removed from the developer and washed with water for about 1 minute.
  • the resist wiring pattern created after development, L/S ( ⁇ m) (Line and Space) 5 ⁇ m/5 ⁇ m, 30 lines, is observed at a magnification of about 800 to 3000 using a scanning electron microscope (SEM).
  • Fine wiring area defect evaluation Regarding the 10 fine wiring resist wiring formation samples obtained in the previous section (i), wiring across multiple wirings regarding the 30 wiring pattern areas formed in each sample.
  • the number of sheets with area defects of 100 ⁇ m or more in circle equivalent diameter where shape defects occur is confirmed, and the following evaluation is performed based on the number of sheets.
  • C The number of samples with area defects is 4 or more and 6 or less.
  • D 7 or more samples with area defects.
  • Fine wiring pinhole defect Regarding the 10 fine wiring resist wiring formation samples used for the evaluation in the previous section (ii), the wiring pattern was 1.5 ⁇ m with respect to the 30 resist wiring patterns formed in each sample. The number of wiring patterns in which missing portions are present is confirmed, and the average value thereof is used to evaluate fine wiring pinhole defects in the film as follows.
  • C The average number of pinhole defects is 6 or more and 10 or less.
  • D The average 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 fine wiring resist shape (8 ⁇ m width) of the film is evaluated as follows using the average value.
  • S The average number of chips is 1 or less.
  • A The average number of chips is 2 or more and 3 or less.
  • B The average number of chips is 4 or more and 7 or less.
  • C The average number of chips is 8 or more and 10 or less.
  • D The average number of chips is 11 or more.
  • a to C are good, and A is the best among them.
  • the fine wiring resist shape (3 ⁇ m width) of the film is evaluated as follows using the average value.
  • S The average number of chips is 1 or less.
  • A The average number of chips is 2 or more and 3 or less.
  • B The average number of chips is 4 or more and 7 or less.
  • C The average number of chips is 8 or more and 10 or less.
  • D The average number of chips is 11 or more.
  • a to C are good, and A is the best among them.
  • PET-1 Terephthalic acid and ethylene glycol were polymerized by a conventional method using antimony trioxide as a catalyst to obtain 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.
  • the obtained polyester pellets were dried and crystallized at 160°C for 6 hours, and then solid phase polymerization was performed at 220°C and a vacuum degree of 0.3 Torr for 8 hours to obtain solid phase polymerized PET (PET-1).
  • PET-1 solid phase polymerized PET
  • the obtained solid phase polymerized PET had a glass transition temperature of 81°C, a melting point of 255°C, and an intrinsic viscosity of 0.61.
  • PET-2 solid phase polymerized PET resin pellets (PET-2) having a glass transition temperature of 81 °C, a melting point of 255 °C, and an intrinsic viscosity of 0.56 were prepared. Obtained.
  • alumina particles (alumina-1) with an average primary particle diameter of 20 nm dispersed in ethylene glycol were added so that the amount added to PET was 2% by mass. After high-precision filtration with a filter that captures 95% or more of foreign matter of 5 ⁇ m or more, the particles were added to obtain particle master pellets MB-A.
  • the obtained particle master pellet MB-A had a glass transition temperature of 80°C, a melting point of 255°C, and an intrinsic viscosity of 0.59.
  • ⁇ Acrylic resin (a-2) In a stainless steel reaction vessel, 75 parts by mass of methyl methacrylate (a), 20 parts by mass of hydroxyethyl methacrylate (b), urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., Art Resin (registered trademark) UN-3320HA, acryloyl The number of groups is 6) (c) is prepared in a ratio of parts by mass, and sodium dodecylbenzenesulfonate is added as an emulsifier in an amount of 2 parts by mass based on the total of 100 parts by mass of the above (a) to (c), and stirred. Mixture 1 was prepared.
  • a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was prepared.
  • 60 parts by weight of the above mixed solution 1, 200 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate as a polymerization initiator were charged into a reactor and heated to 60° C. to prepare a mixed solution 2.
  • Mixed liquid 2 was kept heated at 60° C. for 20 minutes.
  • a mixed liquid 3 was prepared, which consisted of 40 parts by weight of the mixed liquid 1, 50 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate. Subsequently, mixed liquid 3 was dropped into mixed liquid 2 over 2 hours using a dropping funnel to prepare mixed liquid 4.
  • the mixture 4 was kept heated at 60° C. for 2 hours.
  • the obtained mixed liquid 4 was cooled to 50° C. or lower, it was transferred to a container equipped with a stirrer and pressure reduction equipment. 60 parts by weight of ammonia water with a concentration of 25% by weight and 900 parts by weight of pure water were added thereto, and the isopropyl alcohol and unreacted monomers were recovered under reduced pressure while heating to 60°C. Resin (a-2) was obtained and used.
  • ⁇ Acrylic resin (a-3) Dispersion of a water-dispersible acrylic copolymer (glass transition temperature 80°C) consisting of methyl methacrylate/ethyl ethacrylate/acrylic acid/N-methylol acrylamide in water using the method described in the acrylic resin (a-2). (average particle diameter: 110 nm, solid content concentration 40%) was used.
  • Particle component (C)] ⁇ Particle (c-1) An aqueous dispersion of silica "Cataroid” (registered trademark) SI-80P (solid content concentration 10% by mass, solvent: water) manufactured by JGC Catalysts & Chemicals Co., Ltd. and having an average primary particle diameter of 80 nm was used. These acrylic resin (a-1), methylolated melamine resin (b-1), particles (c-1), and water as a solvent are mixed together in the proportions shown in Table 2. A mixed solution with a concentration of 3% was obtained.
  • Example 1 After drying PET resin pellets PET-1, PET-2, and particle master pellets MB-A to C at 180°C for 2 and a half hours under reduced pressure, the amounts of P1 layer, P2 layer, and P3 layer whose blending amounts are listed in Table 3. The mixture is blended so that After that, the film was wound through a T-die onto a cooling cast roll maintained at 42° C. using an electrostatic casting method, and cooled and solidified to obtain an unstretched film.
  • high-precision filters that capture 95% or more of foreign matter of 5 ⁇ m or more are used for filter filtration of the P1 and P2 layers
  • high-precision filters that capture 95% or more of foreign matter of 2 ⁇ m or more are used for the P3 layer filtration.
  • the treated unstretched film After passing the treated unstretched film through a static elimination roll whose roll temperature is set to 25°C, it is sequentially subjected to biaxial stretching under the conditions listed in Table 4.
  • 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 biaxially oriented polyester film with 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 4.
  • the film had good productivity, suitability for high-temperature lamination, and suitability for dry film resist.
  • Example 2 to 20 biaxially oriented polyester films were produced under the film forming conditions listed in Tables 2 to 4.
  • Example 12 after the P2 layer and the P3 layer were laminated after melt extrusion, the coating composition A shown in Table 2 was applied to the surface of the P3 layer opposite to the surface on which the P2 layer was provided in the longitudinally stretched film.
  • a P1 layer was provided using an in-line coating method so that the coating thickness after drying was as shown in Table 4, to obtain a biaxially oriented polyester film having a three-layer structure (P1 layer/P3 layer/P2 layer structure).
  • Examples 19 and 20 were coated after drying using an in-line coating method in the same manner as in Example 12, except that the coating compositions were changed to coating composition B and coating composition C, respectively, as shown in Table 3.
  • a biaxially oriented polyester film having a three-layer structure (P1 layer/P3 layer/P2 layer structure) was obtained, in which the P1 layer was provided so that the film thickness was as shown in Table 4.
  • the structure and film properties of the obtained biaxially oriented polyester film were as shown in Tables 5 and 6.
  • Production suitability and use suitability as shown in Table 7, although film productivity, suitability for high-temperature lamination processing, and suitability for dry film resist were equal to or inferior to those of Example 1, the film had no practical problems.
  • Comparative Examples 1 to 5 In Comparative Examples 1 to 5, biaxially oriented polyester films were produced under the film forming conditions listed in Tables 2 to 4. The structure and film properties of the obtained biaxially oriented polyester film were as shown in Tables 5 and 6. As for production suitability and use suitability, as shown in Table 7, the film was significantly inferior to Example 1 in any of film productivity, high temperature lamination suitability, and dry film resist suitability.
  • the biaxially oriented polyester film of the present invention has excellent processing suitability in the high-temperature lamination process of a film for dry film resist. Since it has productivity and good optical properties by controlling the particle size and surface shape, it is suitably used as a support film for dry film resist for fine wiring.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Materials For Photolithography (AREA)
PCT/JP2023/026984 2022-08-05 2023-07-24 ドライフィルムレジスト支持体用二軸配向ポリエステルフィルム Ceased WO2024029384A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2023547192A JPWO2024029384A1 (https=) 2022-08-05 2023-07-24
KR1020247035520A KR20250048175A (ko) 2022-08-05 2023-07-24 드라이 필름 레지스트 지지체용 이축 배향 폴리에스테르 필름
CN202380055747.4A CN119604400A (zh) 2022-08-05 2023-07-24 干膜抗蚀剂支持体用双轴取向聚酯膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022125263 2022-08-05
JP2022-125263 2022-08-05

Publications (1)

Publication Number Publication Date
WO2024029384A1 true WO2024029384A1 (ja) 2024-02-08

Family

ID=89848942

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/026984 Ceased WO2024029384A1 (ja) 2022-08-05 2023-07-24 ドライフィルムレジスト支持体用二軸配向ポリエステルフィルム

Country Status (5)

Country Link
JP (1) JPWO2024029384A1 (https=)
KR (1) KR20250048175A (https=)
CN (1) CN119604400A (https=)
TW (1) TW202415535A (https=)
WO (1) WO2024029384A1 (https=)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018123318A (ja) * 2017-01-31 2018-08-09 東レ株式会社 転写材用二軸配向ポリエステルフィルムロール
JP2021054055A (ja) * 2019-09-27 2021-04-08 東レ株式会社 ドライフィルムレジスト用二軸配向ポリエステルフィルム

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3750828B2 (ja) 1996-07-10 2006-03-01 東レ株式会社 熱転写用リボン
US7147927B2 (en) 2002-06-26 2006-12-12 Eastman Chemical Company Biaxially oriented polyester film and laminates thereof with copper
JP2021054069A (ja) 2019-09-24 2021-04-08 東レ株式会社 熱転写インクリボン用ポリエステルフィルム
JP7415748B2 (ja) 2020-03-31 2024-01-17 三菱ケミカル株式会社 セラミックグリーンシートの支持体用ポリエステルフィルムロール

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018123318A (ja) * 2017-01-31 2018-08-09 東レ株式会社 転写材用二軸配向ポリエステルフィルムロール
JP2021054055A (ja) * 2019-09-27 2021-04-08 東レ株式会社 ドライフィルムレジスト用二軸配向ポリエステルフィルム

Also Published As

Publication number Publication date
JPWO2024029384A1 (https=) 2024-02-08
CN119604400A (zh) 2025-03-11
TW202415535A (zh) 2024-04-16
KR20250048175A (ko) 2025-04-08

Similar Documents

Publication Publication Date Title
JP7543808B2 (ja) ポリエステルフィルム
JP7848525B2 (ja) ドライフィルムレジスト支持体用二軸配向ポリエステルフィルム
JP7532762B2 (ja) ポリエステルフィルム
JP2008239743A (ja) ドライフィルムレジスト支持体用ポリエステルフィルム
TW201927573A (zh) 雙軸配向熱可塑性樹脂薄膜
JP7375548B2 (ja) 二軸配向熱可塑性樹脂フィルム
JP2021109441A (ja) ポリエステルフィルム
JP2019108527A (ja) ポリエステルフィルム
WO2024029384A1 (ja) ドライフィルムレジスト支持体用二軸配向ポリエステルフィルム
JP2022052031A (ja) 二軸配向ポリエステルフィルム
WO2024162016A1 (ja) 二軸配向積層ポリエステルフィルム
JP4285089B2 (ja) フォトレジスト用ポリエステルフィルム
WO2024057778A1 (ja) ドライフィルムレジスト用積層ポリエステルフィルム
JP2024047656A (ja) 二軸配向ポリエステルフィルムおよびその製造方法
WO2023153074A1 (ja) ポリエステル樹脂組成物およびその製造方法、積層ポリエステルフィルム
WO2019123979A1 (ja) 二軸配向積層フィルム
JP2007211073A (ja) 離型用ポリエステルフィルム
JP2022079091A (ja) ポリエステルフィルム
JP7283040B2 (ja) 熱可塑性樹脂フィルム
JPWO1994019722A1 (ja) 写真フィルム用ベースフィルム
WO2023190265A1 (ja) 二軸配向ポリエステルフィルム
JP2025137346A (ja) ドライフィルムレジスト用二軸配向ポリエステルフィルム
JP2024086625A (ja) 二軸配向ポリエステルフィルム
JP2023128687A (ja) 二軸配向ポリエステルフィルム
JP2024009760A (ja) 二軸配向ポリエステルフィルム

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2023547192

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23849939

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202380055747.4

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 202380055747.4

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020247035520

Country of ref document: KR

122 Ep: pct application non-entry in european phase

Ref document number: 23849939

Country of ref document: EP

Kind code of ref document: A1