WO2020105471A1 - Film de résine thermoplastique biorienté - Google Patents

Film de résine thermoplastique biorienté

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Publication number
WO2020105471A1
WO2020105471A1 PCT/JP2019/043829 JP2019043829W WO2020105471A1 WO 2020105471 A1 WO2020105471 A1 WO 2020105471A1 JP 2019043829 W JP2019043829 W JP 2019043829W WO 2020105471 A1 WO2020105471 A1 WO 2020105471A1
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WO
WIPO (PCT)
Prior art keywords
film
biaxially oriented
thermoplastic resin
protrusions
less
Prior art date
Application number
PCT/JP2019/043829
Other languages
English (en)
Japanese (ja)
Inventor
千代敏弘
鈴木維允
東大路卓司
Original Assignee
東レ株式会社
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 東レ株式会社 filed Critical 東レ株式会社
Priority to KR1020217007929A priority Critical patent/KR20210092192A/ko
Priority to CN201980075895.6A priority patent/CN113056360B/zh
Priority to JP2019563302A priority patent/JP7375548B2/ja
Publication of WO2020105471A1 publication Critical patent/WO2020105471A1/fr

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    • 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
    • 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
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • 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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a biaxially oriented thermoplastic resin film having coarse protrusions but fine protrusions on the background.
  • Thermoplastic resins are used in various industrial fields due to their good workability. Products obtained by processing these thermoplastic resins into films play an important role in today's lives such as industrial applications, optical product applications, packaging applications, and magnetic recording tape applications. 2. Description of the Related Art In recent years, electronic information devices have been downsized and highly integrated, and accordingly, films used for manufacturing electronic information devices have been required to have improved processability. In particular, in the production of electronic information devices, many methods are adopted in which another material is laminated on the film surface and the film is subjected to optical processing such as photoresist.
  • the resist laser light used for processing causes light scattering due to the uneven shape of the film surface. It is a common practice to reduce this.
  • a shape transfer defect hereinafter referred to as a transfer defect when the roll is wound onto the opposite surface (magnetic recording layer surface) side is smooth. Is caused, and the smoothness of the magnetic recording layer surface is deteriorated.
  • the film contains particles to ensure winding and transporting properties.
  • the smoothness of the film can be improved and the above-mentioned transfer defects can be prevented.
  • air that has become trapped between the films cannot escape and wrinkles occur in the floating portions, degrading the quality. I have something to do.
  • Patent Document 1 discloses a technique of roughening the surface by using an additive without containing particles in the film.
  • the surface roughness can be uniformly controlled by the content concentration of the additive, but the problem is that the smoothness is significantly reduced due to the generation of coarse foreign substances derived from the additive. become.
  • the shape of the film surface is controlled, and projections are formed while locally having projections with a high projection height to the extent that transfer defects do not occur. It was found that coexistence of projections having a low height makes it possible to achieve both smoothness and windability (hereinafter sometimes referred to as air bleedability).
  • the present invention has the following configurations. That is, [I] A biaxially oriented thermoplastic resin film in which at least one surface satisfies the following (1) and (2).
  • A When the number of protrusions having a height of 10 nm or more measured by non-contact optical roughness measurement is A (pieces / mm 2 ), A is 2.0 ⁇ 10 3 or more and 2.5 ⁇ 10 4 or less.
  • A When the number of protrusions having a height of 1 nm or more and less than 10 nm measured by Atomic Force Microscope (AFM) is B (pieces / mm 2 ), B is 1.8 ⁇ 10 6 or more. It should be 1.0 ⁇ 10 7 or less.
  • A Atomic Force Microscope
  • [V] Dry film The biaxially oriented thermoplastic resin film according to any one of [I] to [III], which is used as a film for a resist support.
  • [VI] The biaxially oriented thermoplastic resin film according to any one of [I] to [III], which is used as a support film for green sheet molding in the step of producing a laminated ceramic capacitor.
  • [VII] The biaxially oriented thermoplastic resin film according to any one of [I] to [III], which is used as a base film for a magnetic recording medium of a coating type digital recording system.
  • the biaxially oriented thermoplastic resin film of the present invention has good smoothness and windability.
  • R 1 nm as measured by a non-contact optical roughness measurement or AFM (Atomic Force Microscope) measurement, R 10 nm, is a conceptual diagram representing R 60 nm. It is a schematic diagram showing one aspect
  • the present invention relates to a biaxially oriented thermoplastic resin film.
  • the thermoplastic resin referred to in the present invention is a resin that exhibits plasticity when heated.
  • Representative resins include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene ⁇ , ⁇ -dicarboxylate, polymers from P-hexahydroxylylene terephthalate, polymers from 1,4 cyclohexanedimethanol, poly-P. -Polyesters having an ester bond in the main chain, represented by ethyleneoxybenzoate, polyarylate, polycarbonate, etc. and their copolymers, and further nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, etc.
  • Polyamides having an admittance in the main chain as represented, polyethylene, polypropylene, ethylene vinyl acetate copolymers, polymethylpentene, polybutene, polyisobutylene, polyolefins mainly composed of only hydrocarbons such as polystyrene.
  • Polyether sulfones PES
  • polyphenylene oxide PPO
  • polyether ether ketone PEEK
  • polyethylene oxide polypropylene oxide
  • polyethers represented by polyoxymethylene polyvinyl chloride, polyvinylidene chloride, Halogenated polymers represented by polyvinylidene fluoride, polychlorotrifluoroethylene and the like
  • PPS polyphenylene sulfide
  • the thermoplastic resin used in the present invention preferably contains polyester, polyolefin, polyphenylene sulfide (PPS), and polyimide (PI) as main components from the viewpoint of transparency and film-forming property, and among them, polyester is particularly preferable. ..
  • the term "main component” as used herein refers to a component that is contained in an amount of more than 50% by mass and 100% by mass or less in 100% by mass of all components of the film.
  • the polyester referred to in the present invention is obtained by polycondensing a dicarboxylic acid constituent component and a diol constituent component.
  • the constituent component means the minimum unit that can be obtained by hydrolyzing polyester.
  • dicarboxylic acid constituent component of the polyester examples include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,8-naphthalene.
  • dicarboxylic acids such as dicarboxylic acid, 4,4′-diphenyldicarboxylic acid and 4,4′-diphenyletherdicarboxylic acid, or ester derivatives thereof.
  • the diol constituting the polyester is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol. And other aliphatic diols, cyclohexanedimethanol, alicyclic diols such as spiroglycol, and a series of a plurality of the above diols.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene-2,6-naphthalene dicarboxylate
  • isophthalic acid as a part of the dicarboxylic acid component of PET.
  • a polyester obtained by copolymerizing naphthalene dicarboxylic acid and a polyester obtained by copolymerizing cyclohexanedimethanol, spiroglycol, and diethyleneglycol in a part of the diol component of PET are preferably used.
  • the biaxially oriented thermoplastic resin film of the present invention needs to be biaxially oriented. Since the film is biaxially oriented, the mechanical strength of the film is improved and wrinkles are less likely to occur, and the winding property can be improved.
  • the biaxial orientation referred to here is one that exhibits a biaxial orientation pattern by wide-angle X-ray diffraction.
  • the biaxially oriented thermoplastic resin film can be generally obtained by stretching an unstretched thermoplastic resin sheet in the sheet longitudinal direction and width direction and then subjecting it to heat treatment to complete the crystal orientation. Details will be described later.
  • At least one surface has a number of protrusions of 10 nm or more measured by a non-contact optical roughness measuring device according to the method described later as A (pieces / mm 2 ), AFM
  • A is 2.0 ⁇ 10 3 or more and 2.5 ⁇ 10 4 or less.
  • B pieces / mm 2
  • B must be 1.8 ⁇ 10 6 or more and 1.0 ⁇ 10 7 or less (hereinafter, A is 2.0 ⁇ 10 3 or more and 2.5 ⁇ or less).
  • the film surface having B of 1.8 ⁇ 10 6 or more and 1.0 ⁇ 10 7 or less may be simply referred to as the surface).
  • the number A (number / mm 2 ) of protrusions having a height of 10 nm or more measured by the non-contact optical roughness measuring device in the present invention reflects the number of protrusions responsible for air release during winding.
  • the contact area the area of contact with other film surfaces
  • the contact area decreases, and a space for air to escape is secured, so that the winding property is improved. Is improved.
  • the number A of projections (pieces / mm 2 ) is too large, the number of high projections increases, which may increase the occurrence of transfer defects.
  • the number A (number / mm 2 ) of protrusions having a height of 10 nm or more is more preferably 3.0 ⁇ 10 3 or more and 2.0 ⁇ 10 4 or less, and further preferably 4.0 ⁇ 10 3 or more and 2.0 ⁇ 10. It is 4 or less.
  • the number B (number / mm 2 ) of protrusions having a height of 1 nm or more and less than 10 nm which is measured by AFM (Atomic Force Microscope) in the present invention, reflects the number of fine protrusions existing in the bare surface portion of the surface. By reducing the contact area between the background portion and the other surface and increasing the escape path of air by the fine projection uneven structure, it has the effect of remarkably promoting the air release property obtained by the projections of 10 nm or more. ..
  • protrusions having a height of 1 nm or more and less than 10 nm since many protrusions having a height of 1 nm or more and less than 10 nm are present in the background portion, it has an effect of reducing friction between films or with a process roll and reducing scratches on the film surface. If the number of protrusions B (pieces / mm 2 ) is too large, the slipperiness of the film may be improved and winding misalignment may occur during winding or during the slitter step thereafter, resulting in poor roll appearance. In addition, when the number of protrusions B (pieces / mm 2 ) is small, the film becomes flat and the contact area with other surfaces increases, deteriorating air release, and air left in the film during film winding This may cause wrinkles and deteriorate the quality.
  • the number B (number / mm 2 ) of protrusions having a height of 1 nm or more and less than 10 nm is more preferably 3.0 ⁇ 10 6
  • a method for increasing the number A (number / mm 2 ) of protrusions having a height of 10 nm or more measured by a non-contact optical roughness measuring device for example, a method of containing particles having a large particle diameter is used. Can be mentioned.
  • a method for increasing the number B (pieces / mm 2 ) of protrusions having a height of 1 nm or more and less than 10 nm measured by AFM (Atomic Force Microscope) for example, a method of containing particles having a small particle diameter can be mentioned. ..
  • the number of protrusions A and B can be controlled within the above range by the method described later.
  • the number C (pieces / mm 2 ) of protrusions having a height of 60 nm or more measured by a non-contact optical roughness measuring instrument on the surface is 90 or less. Is preferred.
  • the number C (number / mm 2 ) of protrusions having a height of 60 nm or more reflects the number of protrusions having a height that causes a transfer defect.
  • the number of protrusions C (pieces / mm 2 ) exceeds 90, many transfer defects occur and the smoothness of the surface opposite to the surface is reduced. Therefore, when such a film is used for magnetic tape, noise is generated. It often happens.
  • the number of protrusions C is more preferably 80 or less.
  • the lower limit value of the number of protrusions C (pieces / mm 2 ) does not particularly exist, and it is most preferable that it is ultimately 0.
  • the method for setting the number A of the protrusions having a height of 10 nm or more measured by a non-contact optical roughness measuring device within the above range is not particularly limited, It is possible to use a method of containing a resin or a method of containing a resin different from the film main component. From the viewpoint of forming uniform protrusions irrespective of the film forming conditions, it is preferable that particles are contained and controlled by the average particle size and content of the contained particles.
  • the particles contained in the biaxially oriented thermoplastic resin film of the present invention are not particularly limited, and either inorganic particles or organic particles may be used, and two or more kinds of particles may be used in combination.
  • the inorganic particles include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, alumina ( ⁇ alumina, ⁇ alumina, ⁇ alumina, ⁇ alumina),
  • examples thereof include mica, mica, titanium mica, zeolite, talc, clay, kaolin, lithium fluoride, calcium fluoride, montmorillonite, zirconia, wet silica, dry silica and colloidal silica.
  • examples thereof include organic particles having acrylic resin, styrene resin, silicone resin, polyimide resin as a constituent component, core-shell type organic particles, and the like.
  • the particle size of the particles is preferably 10 nm or more and 300 nm or less in average primary particle size obtained by the method described below.
  • the average primary particle diameter is less than 10 nm, the cohesive force between particles becomes large, and a coarse aggregate may be formed to exceed the range of the number A of protrusions.
  • the average primary particle diameter exceeds 300 nm, the size of individual protrusions to be formed becomes large, which may exceed the range of the number A of protrusions.
  • a preferable range of the average primary particle diameter of the particles is 15 nm or more and 200 nm or less.
  • the content of the particles contained in the biaxially oriented thermoplastic resin film of the present invention is not limited at times, but in order not to impair the transparency, the content concentration of the particles should be 3.0% by mass or less based on the entire film. Is preferred. If it exceeds 3.0% by mass, even if particles having an average primary particle size in the preferred range are used, the film may be partially clouded and the haze described below may deviate from the preferred range. It is more preferably 2.0% by mass or less, still more preferably 1.0% by mass or less.
  • the biaxially oriented thermoplastic resin film of the present invention has a laminated constitution of two or more layers, and particles are contained only in the layer having the surface, thereby improving the transparency while aiming at the number A of projections. It becomes easy to set the range.
  • the particle content of the layer having a surface is preferably 0.1 to 0.5 mass% with respect to the entire layer having a surface.
  • the biaxially oriented thermoplastic resin film of the present invention has a constitution in which the biaxially oriented thermoplastic resin film of the present invention has three or more layers from the viewpoint of further improving the winding property, and the surface is It is also preferable to adopt a mode in which particles are contained in the outermost surface layer opposite to the layer provided.
  • the average primary particle diameter is preferably 10 nm or more and 100 nm or less. ..
  • the content of particles contained in the outermost layer opposite to the surface is preferably 1.5% by mass or less based on the entire outermost layer.
  • the particle content with respect to the entire biaxially oriented thermoplastic resin film is 3.0% by mass or less as described above, and the particles having the surface layer and the outermost layer on the side opposite to the surface layer are particles.
  • the layer that does not have a surface layer while containing a film include a film that does not substantially contain particles, and such a film has good transparency.
  • the method for setting the number B of protrusions having a height of 1 nm or more and less than 10 nm measured by the AFM within the above range is not particularly limited, but, for example, nanoimprint
  • the atmospheric pressure referred to here is in the range of 700 Torr to 780 Torr.
  • a film to be treated is introduced between the opposing electrode and an earth roll, a plasma-excitable gas is introduced into the apparatus, and a high-frequency voltage is applied between the electrodes to excite the gas into plasma. Glow discharge is performed between the electrodes.
  • the energy of plasma generated by glow discharge breaks the molecular chains on the film surface and vaporizes low molecular weight substances, which causes the film surface to The phenomenon of being scraped (hereinafter sometimes referred to as decomposition removal) occurs.
  • decomposition removal occurs.
  • the surface of the film is finely processed (disassembled and removed) to form protrusions.
  • Plasma-excitable gas means a gas that can be plasma-excited under the above conditions.
  • the plasma-excitable gas include noble gases such as argon, helium, neon, krypton, and xenon, nitrogen, carbon dioxide, oxygen, or fluorocarbons such as tetrafluoromethane, and mixtures thereof.
  • the plasma-excitable gas may be used alone or in combination of two or more kinds at any mixing ratio. From the viewpoint of high activity when excited by plasma, it preferably contains at least one of argon, oxygen and carbon dioxide, and more preferably contains oxygen.
  • the use of a highly active plasma-excitable gas tends to accelerate the decomposition and removal of the film surface and increase the height of the protrusions formed. In some cases, the number A of protrusions having a height of 10 nm or more, which is measured by the roughness measuring device, increases.
  • the frequency of the high frequency voltage in the plasma treatment is preferably in the range of 1 kHz to 100 kHz.
  • the discharge treatment strength (E value) obtained by the following method is preferably in the range of 10 to 2000 W ⁇ min / m 2 from the viewpoint of projection formation, and more preferably 40 to 500 W ⁇ min / m 2 . is there. If the discharge treatment strength (E value) is too low, the protrusions may not be formed sufficiently, and if the discharge treatment strength (E value) is too high, the thermoplastic resin film may be damaged, or decomposition and removal may occur. In some cases, it progresses and a preferable protrusion is not formed.
  • FIG. 1 shows a conceptual diagram showing R 1nm , R 10nm, and R 60nm measured by a non-contact optical roughness measuring device and AFM.
  • the reference plane is the height determined so that the distance from the reference plane on the measurement surface is 0 (a positive value when the distance is higher than the reference surface, a negative value when the distance is lower than the reference surface). Value).
  • thermoplastic resin film especially a film having an amorphous part and a crystalline part such as PET or PEN
  • it is decomposed and removed from the soft amorphous part.
  • the intrinsic viscosity (IV) of the layer having the surface of the thermoplastic resin film of the present invention is preferably 0.50 dl / g or more, and more preferably 0.60 dl / g or more.
  • IV is a number that reflects the length of the molecular chain. A longer molecular chain makes it easier to clearly form a crystal part and an amorphous part in the same molecular chain. It is preferable because it becomes easier to form finer protrusions.
  • IV is less than 0.50 dl / g, crystallization is likely to proceed due to the short molecular chain, which may cause frequent breakage in the stretching step and make film formation difficult.
  • the number A of protrusions tends to increase by nano-dispersing another thermoplastic resin component in the thermoplastic resin forming the film.
  • the intensity of the atmospheric pressure glow discharge treatment in the plasma treatment or the activity of the plasma-excitable gas used in the atmospheric pressure glow discharge treatment is increased, the number B of the protrusions tends to increase.
  • the biaxially oriented thermoplastic resin film of the present invention may have a single film structure or a structure of two or more layers in which other resins are laminated.
  • the P1 layer / P2 layer structure is arranged such that the surface having the protrusion of the P1 layer is the outermost layer.
  • a two-kind three-layer structure P1 layer / P2 layer / P1 layer
  • a different three-layer structure in which another resin is further laminated P1 layer / P2 layer / P3 layer
  • the method for laminating the other resin layers such as the P1 layer, the P2 layer, and the P3 layer is not particularly limited, but the coextrusion method described below or other resin layer raw materials may be added to the extruder during film formation into the extruder.
  • a method of laminating while melt-extruding and extruding from a die (melt-laminating method), a method of laminating films after film formation via an adhesive layer, and the like can be used.
  • a coextrusion method capable of performing is preferably used.
  • the structure of the P2 layer and the P3 layer of the biaxially oriented thermoplastic resin film of the present invention is not particularly limited, but it is preferable that particles are not substantially contained from the viewpoint of ensuring the transparency of the film.
  • the term "substantially free of particles” means that the content of particles in the thermoplastic resin is 500 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less.
  • heat stabilizers, oxidation stabilizers, antistatic agents, organic / inorganic lubricants, nucleating agents, dyes, Additives such as a dispersant, a coupling agent, and a wavelength conversion material may be blended.
  • the thermoplastic resin film of the present invention preferably has a film haze of 0.60% or less when used in applications requiring high light transmittance such as films for dry film resist supports.
  • a film haze of 0.60% or less when used in applications requiring high light transmittance such as films for dry film resist supports.
  • the haze exceeds 0.60%, transmitted light is scattered when the film is used, and for example, in a dry film resist support application, a defect occurs in the resist wiring. It is more preferably 0.50% or less, still more preferably 0.45% or less.
  • thermoplastic resin film of the present invention will be described by taking a biaxially oriented polyester film as an example, but the present invention is not construed as being limited to the products obtained by such an example. ..
  • a conventional polymerization method can be adopted.
  • a dicarboxylic acid component such as terephthalic acid or an ester-forming derivative thereof and a diol component such as ethylene glycol or an ester-forming derivative thereof are subjected to a transesterification reaction or an esterification reaction by a known method, followed by a melt polymerization reaction. It can be obtained by doing. Further, if necessary, the polyester obtained by the melt polymerization reaction may be subjected to a solid phase polymerization reaction at a melting point temperature of the polyester or lower.
  • the biaxially oriented thermoplastic resin film of the present invention can be obtained by a conventionally known production method.
  • the biaxially oriented thermoplastic resin film of the present invention is a method in which a dried raw material is heated and melted in an extruder as necessary, and extruded from a die onto a cooled cast drum to be processed into a sheet (melt casting Method) can be used.
  • the raw material is dissolved in a solvent, and the solution is extruded from a die onto a support such as a cast drum or an endless belt to form a film, and then the solvent is dried and removed from the film layer to be processed into a sheet.
  • a method (solution casting method) or the like can also be used.
  • an extruder is used for each layer constituting the laminated polyester film, the raw materials of each layer are melted, and these are joined together between the extruder and the die.
  • a method (co-extrusion method) of laminating in a molten state in an apparatus, guiding to a die, extruding from the die onto a cast drum and processing into a sheet (coextrusion method) is preferably used.
  • the laminated sheet is contact-cooled and solidified by static electricity on a drum cooled to a surface temperature of 20 ° C. or higher and 60 ° C. or lower to prepare an unstretched sheet.
  • the temperature of the cast drum is more preferably 25 ° C or higher and 60 ° C or lower, and further preferably 30 ° C or higher and 55 ° C or lower. If the temperature is 20 ° C. or less, projections may not be sufficiently formed on the film surface after being irradiated with plasma and biaxially stretched. If it exceeds 60 ° C, the film may stick to the cast drum, and it may be difficult to obtain an unstretched sheet.
  • the unstretched film obtained here is subjected to surface treatment such as plasma treatment by atmospheric pressure glow discharge.
  • surface treatment such as plasma treatment by atmospheric pressure glow discharge.
  • These surface treatments may be performed immediately after obtaining the unstretched film, after slightly stretching, or after stretching in the longitudinal and / or transverse directions, but in the present invention, it is preferable to perform surface treatment on the unstretched film.
  • the surface to be surface-treated may be either the surface in contact with the cast drum (drum surface) or the surface not in contact with the cast drum (non-drum surface).
  • the unstretched film is biaxially stretched and biaxially oriented.
  • a stretching method a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used.
  • the sequential biaxial stretching method in which the film is first stretched in the longitudinal direction and then in the width direction is effective for obtaining the biaxially oriented thermoplastic film of the present invention without stretching breakage.
  • the stretching conditions for biaxially stretching the unstretched film are not particularly limited, but when the biaxially oriented thermoplastic resin film of the present invention contains polyester as a main component, as stretching in the longitudinal direction, It is preferable that the stretched sheet is guided to a roll group heated to 70 ° C. or higher, stretched in the longitudinal direction (longitudinal direction, that is, the sheet advancing direction), and cooled by a roll group at a temperature of 20 to 50 ° C.
  • the lower limit of the heating roll temperature in the stretching in the longitudinal direction is not particularly limited as long as the stretchability of the sheet is not impaired, but it is preferably higher than the glass transition temperature of the polyester resin used.
  • the preferred range of the stretching ratio in the longitudinal direction is 3 to 5 times.
  • a more preferable range is 3 to 4 times. If the stretching ratio in the longitudinal direction is less than 3 times, oriented crystallization does not proceed and the film strength is significantly reduced. On the other hand, when the stretching ratio exceeds 5 times, the oriented crystallization of the polyester resin may be accompanied by the stretching, resulting in brittleness and tearing during film formation.
  • the film is guided to a tenter while holding both ends of the film with clips, and is perpendicular to the longitudinal direction in an atmosphere heated to a temperature of 70 to 160 ° C. It is preferable to stretch the film in a different direction (width direction) 3 to 5 times, and then heat the stretched film to stabilize the internal orientation structure.
  • the heat history temperature received by the film during the heat treatment should be confirmed by the temperature of a minute endothermic peak (sometimes referred to as Tmeta) that appears immediately below the melting point temperature measured by a differential scanning calorimeter (DSC) described later.
  • the temperature set in the tenter is preferably set so that the maximum temperature in the tenter is 200 ° C. or higher and 250 ° C. or lower.
  • the main component is a plastic resin
  • the heat treatment temperature is lower than 200 ° C.
  • the projections formed by the atmospheric pressure glow discharge treatment cannot be sufficiently grown, and as a result, it becomes difficult to form the projections in the preferable range described above.
  • heat treatment is performed at a temperature of higher than 250 ° C., the film may be melted and frequently broken, and productivity may be reduced.
  • a more preferable range is 220 ° C. or higher and 245 ° C. or lower.
  • the range of Tmeta representing the heat history temperature received by the film during the heat treatment is preferably 190 ° C. or higher and 245 ° C. or lower for the reasons described above.
  • a more preferable range is 210 ° C. or higher and 240 ° C. or lower.
  • Relaxation treatment may be performed in the range of 0% to 6% for the purpose of imparting dimensional stability after further heat treatment.
  • the stretching ratio is 3 to 5 times in each of the longitudinal direction and the width direction, and the area ratio (longitudinal stretching ratio ⁇ horizontal stretching ratio) is preferably 9 to 22 times, more preferably 9 to 20 times. preferable.
  • the area ratio is less than 9 times, the durability of the obtained biaxially stretched sheet becomes insufficient, and when the area ratio exceeds 22 times, tearing tends to occur during stretching. ..
  • the sample is set on the stage so that the measurement Y axis is in the longitudinal direction of the sample film (the longitudinal direction is the direction in which the film runs in the film manufacturing process).
  • the surface analysis software MetroPro 8.1.3 built in the roughness measuring instrument sets the cutoff values to 1.65 ⁇ m for High Filter Wavelen and 50.00 ⁇ m for Low Filter Wavelen. ..
  • the Reference Band (bandwidth) is specified as 100 nm, and Peaks at the slice level of 10 nm is converted into units / mm 2 .
  • the same operation was performed in all 80 fields of view, and the average value thereof was defined as the number A (number / mm 2 ) of protrusions having a height of 10 nm or more in the present invention.
  • a numerical value obtained by converting the average value (values in Density row, Mean column) of the protrusion density per 1 ⁇ m 2 per 1 mm 2 when the threshold value of protrusion height (Threshold Height) is 1 nm (R 1nm ) per 1 mm 2 is N 1 nm (number / mm 2), 10nm 1 ⁇ m 2 average protrusion density per in (R 10 nm) numerical value N 10 nm obtained by converting the (density row, the value of the mean column) per 1 mm 2 (pieces / mm 2)
  • the value obtained by the following equation is defined as the number B (pieces / mm 2 ) of the protrusions having a height of the measured image of 1 nm or more and less than 10 nm.
  • B (pieces / mm 2 ) N 1 nm (pieces / mm 2 ) ⁇ N 10 nm (pieces / mm 2 ).
  • the analysis is performed on all 20 measurement images of each sample, and the average value is defined as the number B (pieces / mm 2 ) of protrusions having a height of 1 nm or more and less than 10 nm.
  • AFM measurement method ⁇ Device: Atomic force microscope (AFM) manufactured by Bruker DIMENSION Icon with ScanAsyst ⁇ Cantilever: Silicon Nitride Probe ScanAsyst Air ⁇ Scan mode: ScanAsyst ⁇ Scanning speed: 0.977Hz -Scanning direction: Scanning is performed in the width direction of the measurement sample manufactured by the method described later.
  • FAM Atomic force microscope
  • Sample measurement frequency Change the location so that each sample is at least 5 ⁇ m or more, and perform 20 measurements.
  • the cross section of the biaxially oriented thermoplastic resin film of the present invention is observed at 10,000 times using a transmission electron microscope (TEM). At this time, when particles of 200 nm or less are confirmed in the observation visual field, the TEM observation magnification is changed to 100,000 times for observation. 100 fields of view were measured at different locations, and the equivalent circle equivalent diameters of all the dispersed particles taken in the photograph were obtained, and the equivalent circle equivalent diameter was plotted on the horizontal axis and the number distribution of particles was plotted on the vertical axis, The equivalent circle equivalent diameter of the peak value was defined as the average primary particle diameter of the particles.
  • TEM transmission electron microscope
  • the number distribution of the equivalent circle equivalent diameter is a distribution having two or more peaks.
  • each peak value is the average primary particle diameter of each particle.
  • the particle size of the maximum particle is the particle size of the particle having the maximum particle size in the photograph observed at 10,000 times.
  • the average primary particle diameter of the agglomerated particles is observed at 200,000 times using the above apparatus.
  • the biaxially oriented thermoplastic film of the present invention is set so that the surface having the surface is in contact with the sample table. At this time, the film is set so as to completely cover the hole formed in the sample table. In this state, a load of 1 kg / cm 2 is applied to set the initial degree of reduced pressure (degree of reduced pressure from normal pressure) to 385 mmHg.
  • Air release time is less than 2400 seconds
  • B Air removal time is 2400 seconds or more and less than 2700 seconds
  • C Air removal time is 2700 seconds or more and less than 2900 seconds
  • D Air release time is 2900 seconds or more A to C are good as air deficiency indexes, and A is the best.
  • Intrinsic viscosity of film IV (dL / g)
  • [ ⁇ ] (dL / g) is calculated by the following equation (a), and the obtained value is taken as the intrinsic viscosity (IV).
  • the IV of the layer having the surface (P1 layer) is obtained by shaving only the P1 layer by a conventional method, and measuring by the above-mentioned method.
  • G Amount of terminal carboxyl group (described as COOH amount in the table)
  • the amount of terminal carboxyl groups was measured by the following method according to the method of Maurice. (References M. J. Maurice, F. Huizinga, Anal. Chim. Acta, 22 363 (1960)). 2 g of a measurement sample was dissolved in 50 mL of o-cresol / chloroform (mass ratio 7/3) at a temperature of 80 ° C., and titrated with a 0.05 N KOH / methanol solution to measure the terminal carboxyl group concentration, and equivalent weight / polyester 1 t It was shown by the value of.
  • phenol red was used as an indicator at the time of titration, and the end point of the titration was determined when the color changed from yellow green to pink. If there is insoluble matter such as inorganic particles in the solution in which the measurement sample is dissolved, the solution is filtered to measure the mass of the insoluble matter, and the value obtained by subtracting the mass of the insoluble matter from the measurement sample mass is the measurement sample mass. Was corrected.
  • the biaxially oriented thermoplastic resin film of the present invention is formed into a film having a width of 4.5 m, and continuous winding of 5000 m rolls is performed 10 times. It evaluated as follows.
  • A 1 roll or less with wrinkles among 10 rolls.
  • B 2 rolls with wrinkles out of 10 rolls.
  • C Of 10 rolls, the number of rolls with wrinkles is 3 or more and 4 or less.
  • D Out of 10 rolls, the number of rolls with wrinkles is 5 or more and 6 or less.
  • E Of the 10 rolls, 7 or more rolls have wrinkles.
  • a to D are good, and A is the most excellent.
  • the shape transfer defect of the biaxially oriented thermoplastic resin film of the present invention was evaluated by the following method.
  • the biaxially oriented thermoplastic resin film of the present invention slit to a width of 1 m is conveyed under a tension of 200 N, and the biaxially oriented thermoplastic resin film of the present invention is provided on the side opposite to the surface for forming a non-magnetic layer described later.
  • the coating solution and the coating solution for forming a magnetic layer are applied in multiple layers, and the coating solution for forming a backcoat layer, which will be described later, is applied to the surface side, and further slit to a width of 12.65 mm (1/2 inch) to form a pancake. create.
  • part means “part by mass”.
  • Coating liquid for forming magnetic layer Barium ferrite magnetic powder 100 parts (plate diameter: 20.5 nm, plate thickness: 7.6 nm, Plate ratio: 2.7, Hc: 191 kA / m ( ⁇ 2400 Oe)
  • Particle size 0.015 ⁇ m 0.5 part Stearic acid 0.5 part Butyl stearate 2 parts Methyl ethyl ketone 180 parts Cyclohexanone 100 parts
  • Non-magnetic powder ⁇ -iron oxide 100 parts Average major axis length
  • the coating solution was pumped through a horizontal sand mill containing an amount of 1.0 mm ⁇ zirconia beads filled to 65% of the volume of the dispersion section, and the coating solution was pumped at 2,000 rpm for 120 minutes (substantially staying time in the dispersion section). ), Dispersed.
  • Polyisocyanate was added to the resulting dispersion in an amount of 5.0 parts for the non-magnetic layer paint, 2.5 parts for the magnetic layer paint, 3 parts of methyl ethyl ketone, and a filter having an average pore size of 1 ⁇ m. It filtered using and prepared the coating liquid for nonmagnetic layer formation and the coating liquid for magnetic layer formation, respectively.
  • a coating solution for forming a backcoat layer carbon black average particle size: 17 nm 100 parts, calcium carbonate average particle size: 40 nm 80 parts, ⁇ -alumina average particles) so that the thickness after calendering on the surface side is 0.5 ⁇ m. Size: 200 nm 5 parts of polyurethane resin and polyisocyanate dispersed) were applied. Then, after calendering with a calender at a temperature of 90 ° C. and a linear pressure of 300 kg / cm (294 kN / m), curing was carried out at 65 ° C. for 72 hours.
  • the non-woven fabric and a razor blade were attached to a device having a slitting device and a winding device so that the non-woven fabric and the razor blade were pressed against the magnetic surface, and the surface of the magnetic layer was cleaned by a tape cleaning device to obtain a magnetic tape.
  • the obtained tape stock was slit to a width of 12.65 mm (1/2 inch), and it was assembled in a case for LTO to create a data storage cartridge with a magnetic recording tape length of 960 m.
  • This data storage was recorded in an environment of 23 ° C. and 50% RH using an IBM LTO7 drive (recording wavelength 0.55 ⁇ m), and then the cartridge was stored in an environment of 50 ° C. and 80% RH for 7 days. After the cartridge was stored at room temperature for one day, the full length was reproduced, and the error rate of the signal during reproduction was measured.
  • the error rate is calculated from the error information (number of error bits) output from the drive by the following equation (b).
  • Error rate (error bit number) / (write bit number)
  • A The error rate is less than 1.0 ⁇ 10 ⁇ 6 .
  • the error rate is 1.0 ⁇ 10 ⁇ 6 or more and less than 1.0 ⁇ 10 ⁇ 5 .
  • Error rate is 1.0 ⁇ 10 ⁇ 5 or more and less than 1.0 ⁇ 10 ⁇ 4 .
  • the error rate is 1.0 ⁇ 10 ⁇ 4 or more.
  • a to C are good, and A is the best.
  • the obtained ceramic slurry is applied onto a surface of the release film, on which the release layer is provided in the preceding paragraph a, provided with a release layer, by a die coater so as to have a thickness of 2 ⁇ m, dried, wound, and rolled into a green sheet.
  • Got The green sheet wound up above is unreeled and visually observed in a state where it is not peeled off from the release film to confirm the presence or absence of pinholes and the coating state of the sheet surface and the end portion.
  • the observed area has a width of 300 mm and a length of 500 mm.
  • the green sheet formed on the release film is illuminated with a backlight unit of 1000 lux from the back side, and pinholes due to coating loss or a recessed state due to surface transfer on the back side of the release film are observed.
  • a to C are good for the evaluation of green sheet characteristics, and A is the best.
  • the biaxially oriented thermoplastic resin film of the present invention is laminated so that the surface opposite to the surface is in contact with the resist layer, and using a rubber roller, the biaxially oriented thermoplastic resin film is laminated on the resist layer. Then, a reticle patterned with chromium metal is arranged on the reticle, and the reticle is exposed using an I-line (ultraviolet ray having a peak wavelength of 365 nm) stepper. c. After peeling the polyester film from the resist layer, the resist layer is placed in a container containing the developer N-A5 and development is performed for about 1 minute. Then, it is taken out from the developing solution and washed with water for about 1 minute.
  • I-line ultraviolet ray having a peak wavelength of 365 nm
  • L / S ( ⁇ m) (Line and Space) 10/10 ⁇ m of the resist pattern formed after development were observed with a scanning electron microscope SEM at about 800 to 3000 magnification, and the pattern was not damaged.
  • the number is evaluated as follows. A: The number of chips is 5 or less. B: The number of chips is 6 or more and 10 or less. C: The number of chips is 11 or more and 15 or less. D: The number of chips is 16 or more. For the photoresist evaluation, A to C are good, and A is the best.
  • PET-1 Polymerization was performed from terephthalic acid and ethylene glycol by a conventional method using antimony trioxide as a catalyst to obtain a melt-polymerized PET containing substantially no particles.
  • the obtained melt-polymerized PET had a glass transition temperature of 81 ° C., a melting point of 255 ° C. and an intrinsic viscosity of 0.62.
  • solid phase polymerization was carried out by a conventional method to obtain solid phase polymerized PET.
  • the obtained solid-state polymerized PET had a glass transition temperature of 81 ° C., a melting point of 255 ° C. and an intrinsic viscosity of 0.81.
  • PET-1 and master pellet MB-A were dried under reduced pressure at 180 ° C. for two and a half hours, and then compounded so that the particle content concentration would be the amounts of P1 layer and P2 layer shown in Table 1, and added to each extruder. After being supplied, melt-extruded and filtered with a filter, they are joined so as to be laminated with P1 layer / P2 layer in a feed block, and then electrostatically cast method is applied on a cooling roll kept at 37 ° C through a T die. It was wound around and solidified by cooling to obtain an unstretched film.
  • This unstretched film was introduced between the opposing electrode and an earth roll, nitrogen gas was introduced into the apparatus, and atmospheric pressure glow discharge treatment was performed under the condition that the E value was 160 W ⁇ min / m 2 .
  • the unstretched film after the treatment was sequentially stretched by a biaxial stretching machine under the conditions shown in Tables 1 and 2 by a stretching ratio of 3.6 times in the longitudinal direction and 4.0 times in the width direction, for a total of 14.4 times. Then, it heat-processed at 240 degreeC under fixed length. Then, relaxation treatment was applied in the width direction to obtain a biaxially oriented film having a thickness of 4.5 ⁇ m.
  • Tables 3 and 4 show the physical properties, surface projection shape and characteristic evaluation of the obtained biaxially oriented film. The film had good winding properties, winding appearance, and transfer defects.
  • Example 2-4 a biaxially oriented film having a thickness of 4.5 ⁇ m was obtained in the same manner as in Example 1 except that the master pellet used was changed to have the particle content concentration shown in Table 1.
  • Tables 3 and 4 show the physical properties, surface projection shape and characteristic evaluation of the obtained biaxially oriented film.
  • Example 2 when a large amount of particles having an average primary particle diameter of 250 nm, which is larger than that in Example 1, was added, the number of protrusions having a height of 10 nm or more measured by non-contact optical roughness measurement increased.
  • the transfer defect was lower than that in Example 1, but was within the practical range, and the film was good in winding property and winding deviation.
  • Example 3 when particles having an average primary particle diameter of 15 nm and 10 nm, which are smaller than those in Example 1, were used, the number of protrusions having a height of 10 nm or more measured by non-contact optical roughness measurement decreased.
  • the winding property was worse than that of Example 1, and the number of protrusions having a height of 1 nm or more and less than 10 nm measured by AFM was increased and the winding appearance was worse than that of Example 1 due to winding misalignment. And the transfer defect was a good film.
  • Example 5 a biaxially oriented film having a thickness of 4.5 ⁇ m was obtained in the same manner as in Example 1 except that the atmospheric pressure glow discharge treatment was performed under the condition that the E value was 450 W ⁇ min / m 2 as shown in Table 2. It was Tables 3 and 4 show the physical properties, surface projection shape and characteristic evaluation of the obtained biaxially oriented film. In comparison with Example 1, Example 5 has an increase in the number of protrusions having a height of 1 nm or more and less than 10 nm measured by AFM, which is within the practical range although the winding shape deteriorates due to winding deviation, and the winding property is improved. The transfer defect was a good film.
  • Example 6 and 7 were the same as Example 1 except that the master pellets used were changed to have the particle addition concentrations shown in Table 1 and the atmospheric pressure glow discharge treatment was changed as shown in Table 2. As a result, a biaxially oriented film having a thickness of 4.5 ⁇ m was obtained. Tables 3 and 4 show the physical properties, surface projection shape and characteristic evaluation of the obtained biaxially oriented film. In Examples 6 and 7, the number of protrusions having a height of 1 nm or more and less than 10 nm measured by AFM was smaller than that in Example 1.
  • Example 6 the number of protrusions having a height of 10 nm or more measured by the non-contact optical roughness measurement was the same as that in Example 1, and the winding property was worse than that of Example 1 although it was within the practical range.
  • Example 7 the number of protrusions having a height of 10 nm or more measured by the non-contact optical roughness measurement was larger than that in Example 1, and thus the winding property was as good as in Example 1.
  • the transfer defect was worse than that of Example 1 within the range of practical use.
  • Example 8 and 9 a biaxially oriented film having a thickness of 4.5 ⁇ m was obtained in the same manner as in Example 1, except that the master pellet used was changed to have the particle addition concentration shown in Table 1.
  • Tables 3 and 4 show the physical properties, surface projection shape and characteristic evaluation of the obtained biaxially oriented film.
  • the number of protrusions having a height of 10 nm or more measured by the non-contact optical roughness measurement and the number of protrusions having a height of 1 nm or more and less than 10 nm measured by AFM are in the preferable ranges.
  • Example 10 A biaxially oriented film was obtained in the same manner as in Example 3 except that the gas species used in the atmospheric pressure glow discharge treatment was a gas obtained by mixing 0.5% by volume of oxygen gas with nitrogen gas.
  • the physical properties, surface projection shape and property evaluation of the obtained biaxially oriented film are as shown in Tables 3 and 4. Since the plasma-excitable gas with high activity was used in Example 10, the number A of protrusions increased as compared with Example 3 due to an increase in the size of the protrusions derived from the added particles, and a film having good winding properties and transfer defects. Became.
  • Example 11 A biaxially oriented film was obtained in the same manner as in Example 1 except that the film thickness was 25 ⁇ m.
  • the physical properties, surface projection shape and property evaluation of the obtained biaxially oriented film are as shown in Tables 3 and 4.
  • the film of Example 11 was as good as that of Example 1 in terms of winding property, winding shape, and transfer defect.
  • the green sheet evaluation and the photoresist evaluation were performed on the film of Example 11 by the method described above, the haze slightly increased as compared with Example 1 due to an increase in the film thickness, but both were good as shown in Tables 5 and 6.
  • Example 12 Except that each layer was extruded with the composition shown in Table 1 by using three kinds of extruders and laminated so as to have a different three-layer constitution of P1 layer / P2 layer / P3 layer, and the film thickness was 25 ⁇ m.
  • a biaxially oriented film was obtained in the same manner as in 1.
  • the physical properties, surface projection shape and property evaluation of the obtained biaxially oriented film are as shown in Tables 3 and 4.
  • Example 12 a film having good winding appearance and transfer defects as in Example 1 was obtained, and further, by providing a P3 layer containing particles on the outermost surface opposite to the surface, the winding property was improved. It was a film superior to 1.
  • the photoresist evaluation was lowered because the haze was increased as compared with Example 11 by providing the P3 layer containing particles.
  • it is within the practical range, and can be suitably used as a film for a dry film resist support or a film for a green sheet support.
  • Example 1 After obtaining an unstretched film in the same manner as in Example 1, a biaxially oriented film was obtained in the same manner as in Example 1 except that the unstretched film was sequentially introduced into a biaxial stretching machine without performing atmospheric pressure glow discharge treatment. Obtained.
  • the physical properties, surface projection shape and property evaluation of the obtained biaxially oriented film are as shown in Tables 3 and 4. Since the atmospheric pressure glow discharge treatment was not carried out, the number of protrusions having a height of 1 nm or more and less than 10 nm measured by AFM was significantly reduced, and as a result, the film was significantly inferior in windability.
  • Example 2 A biaxially oriented film was obtained in the same manner as in Example 1 except that the P1 layer contained substantially no particles.
  • the physical properties, surface projection shape and property evaluation of the obtained biaxially oriented film are as shown in Tables 3 and 4. Since particles are not added, protrusions are efficiently formed on the background, and the number of protrusions with a height of 1 nm or more and less than 10 nm measured by AFM increases, but measured by non-contact optical roughness measurement. The number of projections having a height of 10 nm or more was significantly reduced, and the winding property was lowered, and as a result, the film was significantly inferior in the winding property.
  • Example 3 A biaxially oriented film was obtained in the same manner as in Example 1 except that the average primary particle diameter of the particles added from Example 1 was 350 nm as shown in Table 1.
  • the physical properties, surface projection shape and property evaluation of the obtained biaxially oriented film are as shown in Tables 3 and 4.
  • PET-1 as a raw material for the P1 layer and sodium stearate (crystal nucleating agent-1) which is a crystal nucleating agent were mixed in the amounts shown in Table 1, and the two were sequentially added without performing atmospheric pressure glow discharge treatment.
  • a biaxially oriented film was obtained in the same manner as in Example 1 except that the biaxially oriented film was introduced into the axial stretching machine.
  • Tables 4 and 5 show the physical properties, surface projection shape and characteristic evaluation of the obtained biaxially oriented film.
  • Comparative Example 4 by adding the crystal nucleating agent, the number of protrusions having a height of 1 nm or more and less than 10 nm measured by AFM was significantly reduced as compared with Example 1, and the winding property was significantly deteriorated.
  • Comparative example 5 A biaxially oriented film was obtained in the same manner as in Comparative Example 1 except that the film thickness was 25 ⁇ m.
  • the physical properties, surface projection shape, and characteristic evaluation of the obtained biaxially oriented film are as shown in Tables 3 and 4.
  • Comparative Example 5 was a film in which the winding property was significantly inferior to that of Comparative Example 1.
  • the green sheet evaluation and the photoresist evaluation were performed on the film of Comparative Example 5 by the method described above, wrinkles and scratches were generated on the film surface due to poor winding property and the haze of the film was increased.
  • Tables 5 and 6 the green sheet evaluation and the photoresist evaluation were significantly deteriorated.
  • thermoplastic resin film of the present invention has good transparency, smoothness, and slipperiness, and can further improve scratch resistance in the film forming / processing step. It can be suitably used as a dry film resist support polyester film, an optical device substrate film, a ceramic capacitor release film, or a magnetic recording medium film to be used.
  • P1 layer Layer that has been processed to form protrusions
  • Reference plane (height 0 nm) for non-contact optical roughness measurement and AFM measurement 3.
  • Height 1nm line (R 1nm ) 4.
  • Height 10nm line (R 10nm ) 5.
  • Height 60nm line (R 60nm ) 6.
  • P2 layer 7. P3 layer

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Abstract

L'invention concerne un film de résine thermoplastique biorienté, dont au moins une surface remplit les conditions suivantes (1) et (2), et qui présente un lissé et une aptitude au bobinage appropriés. (1) Lorsque la densité de projection pour des projections ayant une hauteur d'au moins 10 nm, telle que mesurée par mesure de rugosité optique sans contact, est désignée par A (projections/mm2), A est 2.0×103 à 2.5×104. (2) Lorsque la densité de projection pour des projections ayant une hauteur d'au moins 1 nm mais inférieure à 10 nm, telle que mesurée par microscopie à force atomique (AFM), est désignée par B (projections/mm2), B est 1.8×106 à 1.0×107.
PCT/JP2019/043829 2018-11-19 2019-11-08 Film de résine thermoplastique biorienté WO2020105471A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2022000684A (ja) * 2020-06-17 2022-01-04 富士フイルム株式会社 導電性パターンの形成方法、メタルメッシュセンサーの製造方法、及び、構造体の製造方法
WO2023120548A1 (fr) * 2021-12-22 2023-06-29 三菱ケミカル株式会社 Film de polyester et film de polyester stratifié

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JP4975504B2 (ja) * 2006-04-13 2012-07-11 富士フイルム株式会社 透明熱可塑性フィルムおよびその製造方法
KR102204965B1 (ko) * 2013-09-30 2021-01-19 코오롱인더스트리 주식회사 이형필름 및 이의 제조방법
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WO1994013463A1 (fr) * 1992-12-09 1994-06-23 Hoechst Aktiengesellschaft Film de polyester oriente biaxalement ameliore pour support d'enregistrement magnetique
JP2001114913A (ja) * 1994-08-19 2001-04-24 Asahi Kasei Corp 芳香族ポリアミドフィルムおよびその用途
JPH11216824A (ja) * 1998-01-30 1999-08-10 Teijin Ltd 磁気記録媒体用ポリエステルフイルム
JP2017200761A (ja) * 2016-04-28 2017-11-09 東レ株式会社 二軸配向積層ポリエステルフィルムおよび磁気記録媒体
WO2017221701A1 (fr) * 2016-06-24 2017-12-28 東レ株式会社 Film de résine thermoplastique à orientation biaxiale
JP2019108527A (ja) * 2017-12-18 2019-07-04 東レ株式会社 ポリエステルフィルム
WO2019123990A1 (fr) * 2017-12-20 2019-06-27 東レ株式会社 Film de résine thermoplastique biorienté

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JP2022000684A (ja) * 2020-06-17 2022-01-04 富士フイルム株式会社 導電性パターンの形成方法、メタルメッシュセンサーの製造方法、及び、構造体の製造方法
JP7389071B2 (ja) 2020-06-17 2023-11-29 富士フイルム株式会社 導電性パターンの形成方法、メタルメッシュセンサーの製造方法、及び、構造体の製造方法
WO2023120548A1 (fr) * 2021-12-22 2023-06-29 三菱ケミカル株式会社 Film de polyester et film de polyester stratifié

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