WO2019176692A1 - Rouleau de film de polyester antiadhésif biorienté - Google Patents

Rouleau de film de polyester antiadhésif biorienté Download PDF

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Publication number
WO2019176692A1
WO2019176692A1 PCT/JP2019/008899 JP2019008899W WO2019176692A1 WO 2019176692 A1 WO2019176692 A1 WO 2019176692A1 JP 2019008899 W JP2019008899 W JP 2019008899W WO 2019176692 A1 WO2019176692 A1 WO 2019176692A1
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Prior art keywords
film
biaxially oriented
roll
thickness
polyester film
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PCT/JP2019/008899
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English (en)
Japanese (ja)
Inventor
高木順之
多持洋孝
Original Assignee
東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN201980018027.4A priority Critical patent/CN111868148A/zh
Priority to JP2019540108A priority patent/JP7169551B2/ja
Priority to KR1020207027933A priority patent/KR20200131262A/ko
Publication of WO2019176692A1 publication Critical patent/WO2019176692A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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 release biaxially oriented polyester film roll obtained by winding a release biaxially oriented polyester film excellent in film thickness uniformity during thin film slurry coating.
  • Biaxially oriented polyester films are used in various applications as industrial materials from the viewpoint of mechanical properties, thermal properties, stiffness, and cost. Particularly recently, as process papers related to electronic materials, release films for molding green sheets of multilayer ceramic capacitors, separators for liquid crystal polarizing plates, base materials for dry film resists, base materials for interlayer insulating resin release, etc. It is used for.
  • multilayer ceramic capacitors are becoming increasingly smaller and have higher capacities.
  • release films used in the production of multilayer ceramic capacitors the demand for polyester films with high smoothness, no defects in the film surface and inside, and excellent film flatness has continued to grow as green sheets become thinner. Yes.
  • monolithic ceramic capacitors mounted on automobiles is rapidly expanding due to the expansion of electric vehicle production, IoT (Internet of Things) of automobiles, and the mounting of automatic driving functions on automobiles.
  • IoT Internet of Things
  • the thickness of the slurry that is laminated on the film when it is used as a base material due to uneven thickness of the film and the planar characteristics of the film Is becoming more strictly managed.
  • the thickness unevenness of the film is known as a well-known technique in which a measurement is performed by measuring 15 m in the longitudinal direction and a measurement is performed by measuring a 1 m length every 5 mm. Yes. Further, as shown in Patent Document 2, unevenness in the intensity of light leaking from the polarizing plate in the crossed Nicol method for inspecting the polarizing plate becomes strong and obstructs the inspection, so that the unevenness in thickness needs to be within a predetermined range. . As shown in Patent Document 3, it is known that simultaneous biaxial stretching is carried out to enhance the plane orientation.
  • Miniaturization is achieved by reducing the size of the electrode.
  • the increase in capacity is achieved by reducing the thickness of the green sheet, and the increase in reliability is achieved by improving the dimensional accuracy in the width, length, and thickness directions when electrodes and green sheets are provided.
  • the uniformity of the coating thickness at the time of slurry coating is to minimize the distortion and misalignment of the electrode pattern because each electrode area is fine in the step of performing electrode printing later.
  • requirement regarding minimization of the thickness nonuniformity with respect to a film has become severe.
  • the thickness of the base film over the entire roll length is likely to contribute to the process of applying the slurry thin film while constantly monitoring the slurry thickness and correcting the tilt of the die. Is known.
  • this invention makes it a subject to reduce the thickness nonuniformity of the film over the full length of a roll especially when it is used as a support body at the time of green sheet molding.
  • the present inventors have wound a biaxially oriented polyester film for release having excellent slurry dimensional stability in the longitudinal, width and thickness directions by optimizing the film properties.
  • the obtained biaxially oriented polyester film roll for mold release was found, and the present invention was achieved. That is, the present invention is a biaxially oriented polyester for mold release having a film width of 400 mm or more and a variation ⁇ value ( ⁇ MD ) of 0.15 ⁇ m or less with respect to the average value of the thickness measured continuously in the film longitudinal direction of 10,000 m.
  • ⁇ MD variation ⁇ value
  • the present invention it is possible to reduce the thickness variation at the time of green sheet molding, and to wind up the biaxially oriented polyester film for mold release optimized for the coating property of the ceramic slurry at the time of ultra-thin green sheet molding.
  • a biaxially oriented polyester film roll for mold release can be provided.
  • the biaxially oriented polyester film roll for mold release of the present invention is obtained by winding a biaxially oriented polyester film for mold release (hereinafter sometimes simply referred to as a biaxially oriented polyester film) around a core material such as a core.
  • a biaxially oriented polyester film refers to a state in which an unstretched (unoriented) film is stretched in a two-dimensional direction by a conventional method, and indicates a biaxially oriented pattern by wide-angle X-ray diffraction.
  • sequential biaxial stretching or simultaneous biaxial stretching can be employed.
  • sequential biaxial stretching the process of stretching in the longitudinal direction (longitudinal) and the width direction (transverse) can be performed once in the length-width direction, or twice in the length-width-length-width direction. You can also
  • the polyester in the biaxially oriented polyester film of the present invention is a polyester having dibasic acid and glycol as constituent components, and the aromatic dibasic acid is terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenylsulfone.
  • Dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl ketone dicarboxylic acid, phenylindane dicarboxylic acid, sodium sulfoisophthalic acid, dibromoterephthalic acid and the like can be used.
  • alicyclic dibasic acid oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid and the like can be used.
  • glycol ethylene glycol, propylene glycol, tetramethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol and the like can be used as the aliphatic diol, and naphthalenediol, 2,2-bis (4-hydroxydiphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, hydroquinone, etc. can be used.
  • Cyclohexanedimethanol, cyclohexanediol and the like can be used as the alicyclic diol.
  • the polyester can be produced by a known method, and the intrinsic viscosity preferably has a lower limit of 0.5 and an upper limit of 0.8. More preferably, the lower limit is 0.55 and the upper limit is 0.70.
  • ⁇ sp (solution viscosity / solvent viscosity) ⁇ 1
  • C is the dissolved polymer mass per 100 ml of solvent (g / 100 ml, usually 1.2)
  • K is the Huggins constant (assuming 0.343). is there.
  • the solution viscosity and solvent viscosity are measured using an Ostwald viscometer. The unit is indicated by [dl / g].
  • the biaxially oriented polyester film of the present invention may be a single layer film or a laminated structure of two or more layers.
  • it consists of a polyester A layer and a polyester B layer.
  • it consists of a polyester A layer, a polyester B layer and a polyester C layer, or a polyester A layer, a polyester B layer and a polyester A layer. It becomes the laminated film which becomes.
  • the recovered raw material of the edge part generated in the film forming process can be used by mixing recycled raw materials for other film forming processes in a timely manner, and it is possible to reduce the consumption of petroleum resources and to obtain cost merit. This is the most preferred embodiment.
  • the biaxially oriented polyester film of the present invention contains a recovered raw material and / or a recycled raw material in the C layer. Therefore, the C layer is preferably the thickest layer in the layer configuration.
  • the melting specific resistance of the raw material contained in the A layer is preferably 1.0 ⁇ 10 6 ⁇ ⁇ cm or more and 1.0 ⁇ 10 8 ⁇ ⁇ cm or less, and more preferably 5.0. ⁇ 10 8 ⁇ ⁇ cm or less is preferable. It is also preferred that the raw material having such a melt specific resistance value is a polyester resin.
  • the A layer is preferably a layer constituting a surface whose SRa (A) described later is 1 nm or more and less than 15 nm.
  • the aspect which has the characteristic regarding the raw material composition and thickness of C layer mentioned above, the characteristic regarding the raw material of A layer, and the characteristic regarding a surface shape is also preferable.
  • the surface of the two layers constituting the surface layer of the two or more layers that is, the surface of the polyester A layer and the polyester B layer, the surface smoothness and handling such as conveyance and winding.
  • the center line roughness SRa (A) of one film surface is 1 nm or more and less than 15 nm
  • the center line roughness SRa (B) of the other film surface is 20 nm or more and 40 nm or less.
  • SRa (A) When SRa (A) is less than 1 nm, peeling may be difficult in a peeling step after a release layer is laminated on the surface and a ceramic slurry is laminated thereon. On the other hand, when SRa (A) is 15 nm or more, the surface state of the slurry is deteriorated and the thickness is uneven, and as a result, the characteristics of the capacitor are likely to vary. When SRa (B) is less than 20 nm, blocking is likely to occur during winding after the release layer is applied or winding after applying the ceramic slurry, and charging may occur when it is fed out.
  • the center line roughness SRa (A) of one film surface is more preferably 2 nm or more and less than 12 nm, and the center line roughness SRa (B) of the other film surface is more preferably. Is 25 nm or more and 35 nm or less.
  • the thickness of the biaxially oriented polyester film of the present invention is preferably 12 ⁇ m or more, more preferably 20 ⁇ m or more, and further preferably 25 ⁇ m or more. Moreover, it is preferable that it is 188 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 40 micrometers or less. When the thickness is less than 12 ⁇ m, there is no support for holding the ceramic slurry, and the ceramic slurry cannot be supported in the application of the ceramic slurry, and uniform drying cannot be performed in the subsequent process, and thermal wrinkle is not sufficiently suppressed. It may become.
  • a preferable range of the thickness is 12 ⁇ m or more and 188 ⁇ m or less, more preferably 20 ⁇ m or more and 50 ⁇ m or less, and further preferably 25 ⁇ m or more and 40 ⁇ m or less.
  • the biaxially oriented polyester film of the present invention may contain particles.
  • the volume average particle size of the particles contained at this time is preferably 1.3 ⁇ m or less. If the volume average particle diameter of the particles exceeds 1.3 ⁇ m, there is a high chance that voids, that is, voids, are generated at the interface between the particles and the polymer at the time of stretching.
  • the thickness variation may increase.
  • the ultra-thin green sheet in the present invention refers to a sheet having a thickness of less than 1 ⁇ m.
  • the particles used in the present invention are inorganic particles such as spherical silica, agglomerated silica, calcium carbonate, aluminum oxide, barium titanate, and titanium oxide, crosslinked polystyrene resin particles, crosslinked silicone resin particles, crosslinked acrylic resin particles, and crosslinked styrene-acrylic resin.
  • Organic particles such as particles, crosslinked polyester particles, polyimide particles, and melamine resin particles can be used. In addition to the role of forming protrusions on the film surface, these particles can also serve as a core material for forming voids, so it is desirable to select the type of particles together with the particle diameter.
  • organic particles having high particle elasticity are used.
  • the organic particles are particularly preferably organic particles selected from crosslinked polystyrene resin particles, crosslinked silicone resin particles, crosslinked acrylic resin particles, crosslinked styrene-acrylic resin particles, and crosslinked polyester particles.
  • organic particles selected from crosslinked polystyrene resin particles, crosslinked silicone resin particles, crosslinked acrylic resin particles, crosslinked styrene-acrylic resin particles, and crosslinked polyester particles.
  • spherical silica and aluminum oxide are particularly preferable.
  • the particle shape and particle size distribution are preferably uniform, and in particular, the particle shape is preferably close to a sphere.
  • V is the particle volume ( ⁇ m 3 )
  • Dm is the maximum diameter ( ⁇ m) on the projection plane of the particles.
  • cross-linked polystyrene resin particles, cross-linked silicone resin particles, and cross-linked acrylic resin particles synthesized by an emulsion polymerization method and the like can be suitably used.
  • cross-linked polystyrene particles, cross-linked silicone, and spherical silica have a volume shape factor. It is close to a true sphere, and the particle size distribution is extremely uniform, which is preferable from the viewpoint of uniformly forming film surface protrusions.
  • the biaxially oriented polyester film of the present invention has a film width of 400 mm or more and a variation ⁇ value ( ⁇ MD ) of 0.15 ⁇ m or less with respect to the average value of thicknesses measured continuously in the film longitudinal direction of 10,000 m.
  • the biaxially oriented polyester film of the present invention has a film width of 400 mm or more and a variation ⁇ value ( ⁇ MD ) of 0.15 ⁇ m or less with respect to the average value of thicknesses measured continuously in the film longitudinal direction of 10,000 m.
  • the thickness continuously measured in the film longitudinal direction of 10,000 m here is the thickness when the film is continuously measured in a non-contact manner.
  • the film width and the length in the longitudinal direction represent the dimensions of the support necessary for manufacturing the multilayer ceramic capacitor in a certain lot. That is, it has been found that the green sheet moldability can be improved by suppressing variations in thickness within these dimensions.
  • the ⁇ MD value is sometimes referred to as uneven film thickness in the longitudinal direction.
  • the thickness of a conventional biaxially oriented polyester film is measured by scanning a non-contact thickness meter in the width direction while the film is being formed, or by collecting a sample taken about 20 m in the longitudinal direction from a film roll.
  • the thickness unevenness behavior that could not be confirmed in the past was found by continuously measuring in the longitudinal direction of 10,000 m as described above.
  • the present invention has the effects of reducing the uneven thickness of the slurry when applying the thin film ceramic slurry, reducing the variation in capacitance, and suppressing the probability of short circuit.
  • sigma MD is more than 0.15 [mu] m, the effect of uneven thickness of the slurry is increased above is reduced in the coating of thin ceramic slurry.
  • the center line roughness SRa (A) of one film surface is 1 nm or more and less than 15 nm
  • the center line roughness SRa (B) of the other film surface is 20 nm or more and 40 nm or less.
  • the biaxially oriented polyester film of the present invention can be subjected to mold release treatment on both surfaces in consideration of the balance between slurry coating thickness and handling properties, and can be planarized before mold release treatment. To reduce the roughness of the release layer surface.
  • inert particles are dispersed in a predetermined proportion in ethylene glycol which is a diol component, and this ethylene glycol slurry is added at an arbitrary stage before completion of polyester polymerization.
  • ethylene glycol which is a diol component
  • this ethylene glycol slurry is added at an arbitrary stage before completion of polyester polymerization.
  • a method in which a water slurry of particles is directly mixed with a predetermined polyester pellet, supplied to a vent type twin-screw kneading extruder, and kneaded into the polyester is also effective for the production of the present invention.
  • the thus prepared particle-containing master pellets and pellets substantially free of particles and the like are mixed at a predetermined ratio, dried, and then supplied to a known melt laminating extruder.
  • a uniaxial or biaxial extruder can be used as the extruder for producing the biaxially oriented polyester film of the present invention.
  • the vent type extruder which provided the vacuum drawing line in the extruder can also be used.
  • what is called a tandem extruder which shares the function which melt
  • a tandem extruder is preferable as a process for reducing unevenness in thickness because the polymer temperature at the time of high discharge can be stabilized, and as a result, the viscosity variation of the polymer can be reduced.
  • the polymer melted and extruded by the extruder is filtered through a filter.
  • a filter having a high collection efficiency that collects 95% or more of a foreign substance having a size of 3 ⁇ m or more On the other hand, if the collection efficiency of the filter is too high, the degree of pressure increase may increase. Therefore, a filter with a higher accuracy of collection efficiency that collects 95% or more of foreign matters less than 3 ⁇ m. Use may be an unfavorable embodiment in reducing thickness unevenness.
  • the sheet is extruded from a slit-shaped slit die and cooled and solidified on a casting roll to form an unstretched film.
  • lamination is performed in three layers using three extruders, a three-layer manifold or a merge block (for example, a merge block having a rectangular merge portion), and a sheet is extruded from a die.
  • the base of the base can be automatically adjusted with a heater.
  • the sheet extruded from the die is cooled by a casting roll to form an unstretched film.
  • a method of installing a static mixer and gear pump in the polymer flow channel is effective as a means for suppressing uneven thickness in the longitudinal direction in the present invention. Since the gear pump has a function of blocking pressure fluctuations in the extrusion process, it is necessary to uniformly control the thickness in the longitudinal direction. By making the rotational speed of the gear built in the gear pump constant, uneven thickness in the longitudinal direction is required. Can be kept small. In the present invention, it is also effective to control the rotation speed of the gear pump by feeding back the weight-converted thickness of the rolled up intermediate product. This is because the discharge decreases as the filter pressure increases, and the film thickness gradually decreases in the longitudinal direction.
  • the ⁇ MD value in order to control the ⁇ MD value, it was necessary to further improve the accuracy, so when evaluating the rotation accuracy of the casting roll, it was measured by a sensor installed on the ground on which the casting drum was installed, The difference between the maximum value and the minimum value of the uneven state when the distance from the sensor to the cast surface was measured for one round on the cast circumference was defined as a shake.
  • the numerical value is desirably within 50 ⁇ m, and further within 30 ⁇ m is a desirable form in order to improve the thickness unevenness ( ⁇ MD ) in the longitudinal direction in the present invention.
  • the unevenness of the cast circle around the cast circle is measured by installing a laser displacement meter on the floor where the casting device is installed, and measuring the distance between the casting roll and the measurement unit of the laser displacement meter. .
  • the unstretched film that has landed on the casting roll is brought into close contact with the cast using electrostatic force using a pinning device.
  • the pinning device applies electric charges from the electrostatic application wire to the casting roll over the entire width of the unstretched film, and causes the film and the casting roll to adhere to each other by static electricity to the interface between the casting roll and the film.
  • the distance from the electrostatic application wire to the film is equal over the entire width of the unstretched film.
  • the end of the unstretched film is adjusted so that the thickness of the end becomes thicker than the center in order to increase the gripping force of the clip when stretched by a transverse stretcher, but the end adhesion is poor and casting As a result of poor cooling efficiency due to the roll, crystallization at the end proceeds and may cause breakage.
  • a so-called edge pinning device that additionally attaches a pinning device only to the end is provided. By attaching, the end of the unstretched film is brought into close contact with the cast, and the uneven cooling of the edge part is also suppressed, so that vibration at the landing point of the cast can be suppressed, and desirable in order to improve the uneven thickness in the longitudinal direction.
  • edge pinning apparatus when applying an edge pinning apparatus to an unstretched film, if it implements from the location 5 mm or more away from the edge part edge part of an unstretched film, effective pinning can be performed. This is to prevent the leakage current from being abnormally discharged to the casting roll during the electrostatic application from the edge pinning device.
  • the processing width of edge pinning is adjusted in accordance with the edge thickness profile of the unstretched film, but setting the range to 20 mm or more and less than 100 mm can effectively mold the edge part.
  • the film that has been in close contact with the casting roll and cooled is peeled off from the casting roll using a pulling roll, and then led to the next stretching step.
  • the separation roll may be subjected to water for cooling the film, or may be driven.
  • the stretching method may be simultaneous biaxial stretching or sequential biaxial stretching.
  • simultaneous biaxial stretching when vertical and horizontal stretching are performed simultaneously, the wind speed variation and the airflow flowing along the film (associated airflow) affect the longitudinal direction as well as the disturbance in the longitudinal direction. This is a form in which stretching is preferably applied.
  • the first stretching in the longitudinal direction is important for suppressing the occurrence of scratches and for suppressing uneven thickness in the longitudinal direction. It is 90 ° C or higher and 130 ° C or lower, preferably 100 ° C or higher and 120 ° C or lower.
  • the stretching temperature is lower than 90 ° C, the film is easily broken, and when the stretching temperature is higher than 130 ° C, the film surface is easily damaged by heat.
  • stretching is preferably performed in two or more stages, and the total magnification is 2.8 times to 5.0 times in the length direction, preferably 3.3 times.
  • the longitudinal stretching ratio is 4.0 times or less and 3.5 times or more and 5 times or less, preferably 4.0 times or more and 4.5 times or less in the width direction.
  • the stretching ratio in one stretching section is 3.0 times or less because an appropriate stretching tension can be secured. If the temperature and magnification range are out of the range, problems such as uneven stretching or film breakage are caused, and it is difficult to obtain a film characterized by the present invention.
  • the stretching process in the longitudinal direction is due to the contact between the film and the roll, and the film is likely to be damaged when the film slips due to the difference between the peripheral speed of the roll and the speed of the film. Therefore, a drive system in which the roll peripheral speed can be individually set for each roll is preferable.
  • the material of the transport roll is heated to a temperature higher than the glass transition point before stretching or transported to the stretching zone while maintaining the temperature below the glass transition point. Either heating or not is selected.
  • adhesiveness due to heating induces stretching unevenness.
  • a conveyance roll As a metal roll plated with hard chrome, it is preferable to set the conveyance temperature to less than 80 ° C. In this case, it is preferable to supplement the amount of heat using an infrared heater in the stretching step.
  • the surface roughness Ra of the stretching roll is 0.005 ⁇ m or more.
  • the thickness is preferably 1.0 ⁇ m or less, more preferably 0.1 ⁇ m or more and 0.6 ⁇ m or less.
  • Ra is larger than 1.0 ⁇ m, the unevenness of the roll surface during stretching is easily transferred to the film surface, and when it is smaller than 0.005 ⁇ m, the roll and the film background adhere to each other, and the film is easily damaged by heat.
  • it is effective to appropriately adjust the particle size of the abrasive and the number of polishings.
  • setting the longitudinal stretching ratio lower than the transverse stretching ratio is a preferable stretching condition in order to reduce the thickness unevenness in the longitudinal direction.
  • the unstretched film is transported to the stretching zone while being kept at a temperature lower than the glass transition point, but when heated at the time of stretching, the preheating zone transport roll was subjected to surface treatment with hard chromium or tungsten carbide. It is preferable to use a metal roll having a surface roughness Ra of 0.2 ⁇ m or more and 0.6 ⁇ m or less in order to suppress adhesion that causes heat wrinkles and uneven thickness in the longitudinal direction.
  • the uniaxially stretched film stretched in the longitudinal direction is heated to 90 ° C. or more and less than 120 ° C. with a transverse stretching machine, and then stretched in the width direction at 3 times or more and less than 6 times to obtain biaxial stretching (biaxial stretching) Orientation) film.
  • This horizontal stretching machine performs self-circulation for each room of the oven and blows warm air on the film to raise the temperature of the film and to perform stretching and heat setting.
  • air is preferably supplied and exhausted in the oven to replace the air.
  • the direction of the air flowing above and below the conveyed film is the same direction as the film flow direction.
  • the air flow inside the STN changes in a complex manner.
  • the flow of air between the chambers may change from, for example, a flow from upstream to downstream to a flow from downstream to upstream.
  • the air flow between the chambers may lead to uneven stretching of the film when the temperature of the air varies between the chambers. For this reason, regarding the conditions of the intake air amount and the exhaust air amount of the oven, the flow of air in the same direction can be induced by making the exhaust air amount larger than the air supply amount.
  • the biaxially oriented polyester film of the present invention may be further re-stretched once or more in each direction, or may be re-stretched simultaneously biaxially.
  • a method for suppressing the thickness unevenness in the longitudinal direction it is possible to relieve the bowing generated in the previous transverse stretching step in the longitudinal re-stretching step.
  • it may be heated at a temperature of 80 ° C. to 100 ° C. with a transport roll before re-longitudinal stretching in the longitudinal direction, or may be transported using an unheated roll.
  • you may pass through a re-longitudinal stretch process, without applying a draw ratio.
  • the heat treatment temperature can usually be an arbitrary temperature of 150 ° C. or higher and lower than 245 ° C., and the heat treatment time is preferably 1 second or longer and 60 seconds or shorter.
  • the heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. Further, after the heat treatment, it is preferable to relax at a temperature lower by 0 ° C. or more and 150 ° C. or less than the heat treatment temperature by 0% or more and 10% or less in the width direction.
  • the film after the heat treatment can be provided with, for example, an intermediate cooling zone or a cooling zone, and the dimensional change rate and flatness can be adjusted.
  • relaxation may be performed in the longitudinal direction and / or the transverse direction during the heat treatment or in the subsequent intermediate cooling zone or cooling zone.
  • the film after biaxial stretching is cooled in the conveying process, and then the edge is cut and wound to obtain an intermediate product.
  • the film thickness in the width direction is measured, the data is fed back and used to adjust the film thickness by adjusting the die thickness and the like, and foreign matter detection by the defect detector can be performed.
  • Thickness can be measured by ⁇ -rays, X-rays, or an optical interference method.
  • Measurement is a method of measuring the full width by traversing one measuring device in the width direction, a method of measuring the full thickness by traversing a plurality of measuring devices in the section divided in the width direction, When the range is wide, a plurality of measuring devices can be fixed in the width direction to measure the thickness of the entire width. Moreover, about the place to measure, it can also carry out offline using the measurement in the said conveyance process, or using the biaxially-oriented polyester film roll after slitting an intermediate product.
  • the intermediate product is slit into an appropriate width and length by a slitting process and wound around a core to obtain a roll of a biaxially oriented polyester film.
  • the core is a cylindrical winding core made of plastic or paper. Since it is preferable to use a core with little expansion and contraction due to temperature and humidity and little deformation due to winding pressure, it is preferable to use a plastic core. Furthermore, it is preferable to use a core in which a plastic is reinforced with glass fiber or carbon fiber. Moreover, when using paper for a core, intensity
  • the film cutting step in the slitting step is a step for removing an unnecessary portion of the intermediate product and obtaining a polyester film roll having a desired product width.
  • this cutting step 3 to 10 locations are simultaneously cut in the width direction of the intermediate product.
  • the method used for this cutting can be selected from a method of cutting by shearing the lower blade and the upper blade and a method of cutting in the air between the pass lines.
  • the film width is the width of the film after slitting by the slitting process, and a polyester film roll having a desired product width can be obtained by adjusting the cutting location in the cutting process described above in the width direction. .
  • the length of the film longitudinal direction in this invention is measured with the length measuring device installed on the arbitrary rolls of a slit process.
  • a polyester film roll in this invention.
  • the film Since the biaxially oriented polyester film roll for mold release obtained by the above-described method winds up a film with little thickness unevenness in the longitudinal direction, the film is used as a mold member for mold release applications, particularly for multilayer ceramic capacitors. Furthermore, it can be more preferably used as a molding member of a laminated ceramic capacitor for automobiles.
  • the mold release use in this invention refers to the use which uses the film obtained from the biaxially-oriented polyester film roll of this invention for a base material as a shaping
  • Examples of the member here include a green sheet in a multilayer ceramic capacitor, an interlayer insulating resin (electrical insulating resin) in a multilayer circuit board, and a polycarbonate (in this case, used in solution casting) in an optical member. Can be mentioned.
  • the measurement method and evaluation method relating to the present invention are as follows.
  • SRa value Film surface roughness Surface centerline roughness (SRa value) Measured using a three-dimensional fine surface shape measuring instrument (ET-350K manufactured by Kosaka Manufacturing Co., Ltd.), and obtained from the surface profile curve, according to JIS B0601 (1994), arithmetic average roughness (centerline roughness) SRa Find the value.
  • the measurement conditions are as follows. X direction measurement length: 0.5mm X direction feed rate: 0.1 mm / sec Y direction feed pitch: 5 ⁇ m Number of lines in Y direction: 40 Cutoff: 0.25mm Stylus pressure: 0.02mN Height (Z direction) magnification: 50,000 times
  • the X direction is measured in the width direction of the sample, and the Y direction is measured in the longitudinal direction of the sample.
  • polyester resin 150 g of polyester resin was put into a 50 ⁇ test tube substituted with pure water, and dried under reduced pressure at 180 ° C. for 3 hours. Then, it melted under nitrogen flow at 290 ° C. for 50 minutes, and the electrode was inserted into the molten polymer. The melt specific resistance was determined by calculating the resistance value from the amount of current when a voltage of 5,000 V was applied between the electrodes.
  • the electrodes were prepared such that a Teflon (registered trademark) spacer was sandwiched between two copper plates (22 cm 2 ) and the distance between the copper plates was 9 mm.
  • Example 1 Preparation of polyester pellets (Preparation of polyester A) Esterification reaction is conducted while distilling water at 255 ° C. with 86.5 parts by mass of terephthalic acid and 37.1 parts by mass of ethylene glycol. After completion of the esterification reaction, 0.02 part by weight of trimethyl phosphate, 0.06 part by weight of magnesium acetate, 0.01 part by weight of lithium acetate, and 0.0085 part by weight of antimony trioxide were added. A polycondensation reaction was carried out by heating up to 0 ° C. and a polyester pellet A having an intrinsic viscosity of 0.63 dl / g was obtained. As a result of measuring the melting specific resistance of this chip, it was 7.0 ⁇ 10 7 ⁇ ⁇ cm.
  • the spherical silica used in polyester B is obtained by adding a mixed solution consisting of ethanol, pure water, and aqueous ammonia as a basic catalyst to this mixed solution while stirring the mixed solution of ethanol and ethyl silicate.
  • the monodispersed silica particles obtained by stirring the reaction solution and conducting a hydrolysis reaction of ethyl silicate and a polycondensation reaction of the hydrolysis product, followed by stirring after the reaction.
  • a water slurry of divinylbenzene / styrene copolymer crosslinked particles having a Mohs hardness of 3 (crosslinking degree of 80%) is contained in the above-mentioned homopolyester pellets substantially free of particles using a vented biaxial kneader, and the volume Master pellets containing 1% by mass of divinylbenzene / styrene copolymer crosslinked particles having an average particle size of 0.3 ⁇ m and 0.8 ⁇ m with respect to the polyester were obtained (Polyester C and Polyester D), respectively.
  • polyester A After transesterification, 10 parts by mass of calcium carbonate and 90 parts by mass of ethylene glycol prepared by the carbon dioxide method (volume average particle size volume average particle size 1.1 ⁇ m, Mohs hardness 3) were wet pulverized. A calcium carbonate / ethylene glycol dispersion slurry was obtained. The volume average particle diameter of this calcium carbonate was 1.1 ⁇ m. On the other hand, 0.04 parts by mass of manganese acetate and 0.03 parts by mass of antimony trioxide are added to 100 parts by mass of dimethyl terephthalate and 64 parts by mass of ethylene glycol as a catalyst, and then a transesterification reaction is performed.
  • the recovered raw material A was obtained by collecting the film after producing the film having the following formulation and pelletizing it.
  • the ratio described below is represented by mass ratio (mass%) with respect to the mass of the whole film.
  • polyester pellets to be supplied to the extruders of the respective layers A, B and C were prepared at the following ratio.
  • the ratio described below is a mass ratio (unit: mass%) with respect to the polyester pellet which comprises each layer.
  • the raw materials for layer A and C are the raw materials after stirring, and the vents for layer A and layer C.
  • the raw material of the B layer was dried under reduced pressure at 160 ° C. for 8 hours and supplied to the single screw extruder for the B layer.
  • the B layer is melt extruded at 275 ° C. with a tandem extruder, filtered with a high-precision filter that collects 95% or more of foreign matters of 3 ⁇ m or more, and then merged and laminated with a rectangular heterogeneous three-layer merge block.
  • a three-layer stack consisting of A, layer B, and layer C was used.
  • the film is wound around a casting drum having a surface temperature of 25 ° C. and cooled and solidified by using an electrostatic application casting method in which electrostatic application is applied to the entire width of the unstretched film through a slit die maintained at 285 ° C. Got. At this time, the cast was aligned, and the deflection was 25 ⁇ m.
  • This uniaxially stretched film was stretched 4.0 times at 115 ° C. in the transverse direction in a stenter, then heat-set at 230 ° C., relaxed by 5% in the width direction, cooled in the conveying process, and then edged.
  • the product was wound up after cutting to obtain an intermediate product of a biaxially stretched film having a thickness of 31 ⁇ m.
  • air supply / exhaust from the outside of the oven was adjusted to allow air to flow in a certain direction.
  • This intermediate product was slit with a slitter to obtain a biaxially stretched film roll having a thickness of 31 ⁇ m.
  • the layer A was 6.5 ⁇ m
  • the layer B was 23.5 ⁇ m
  • the layer C was 1.0 ⁇ m.
  • Data was collected from the obtained products, and the results of characteristic evaluation are shown in Table 1.
  • the obtained ceramic slurry is coated on a release film with a die coater so that the thickness after drying is 0.5 ⁇ m, and dried, and the slurry thickness after drying is a non-contact method at the center of the coating. Was measured continuously. Thereafter, winding was performed to obtain a green sheet. At this time, the slurry thickness unevenness ⁇ value was evaluated. A value less than 0.13 was good, a value between 0.13 and less than 0.15 was acceptable, and a value exceeding 0.15 was regarded as defective. The slurry thickness unevenness in the embodiment of Example 1 was good in green sheet moldability. At this time, good is at a level where there is no practical problem.
  • Example 2 The procedure was the same as in Example 1 except that the film forming conditions such as the draw ratio and thickness were changed. The results obtained are shown in Table 1.
  • Example 5 The center value of the thickness was corrected by decreasing the rotational speed control of the gear pump in accordance with the increase of the polymer filter pressure.
  • the procedure was the same as in Example 1 except that the film forming conditions such as the draw ratio and thickness were changed. The results obtained are shown in Table 1.
  • Example 6 An edge pinning device was applied to the cast sheet. In the pinning, electrostatic application was performed in a range from 5 mm inside to 50 mm inside the unstretched sheet. Film formation was performed under the same conditions as in Example 1. The results obtained are shown in the table.
  • Example 1 The procedure was the same as in Example 1 except that the film forming conditions such as the draw ratio and thickness were changed. The results obtained are shown in Table 2. The slurry thickness unevenness was worse than that of Examples 1 to 4, and the evaluation was acceptable.
  • Example 3 The same operation as in Example 1 was performed except that the longitudinal draw ratio and the transverse draw ratio were changed to 4.5 times and 4.5 times, respectively. By increasing the magnification, but the purpose of flattening unevenness generated in step earlier, resulting sigma MD worsened. As a result of performing frequency analysis of thickness unevenness for ⁇ MD, a period of stretching unevenness that seems to be derived from longitudinal stretching was confirmed.
  • Comparative Example 6 Comparative Example 6
  • the edge pinning device was applied, but there was no improvement effect on the casting failure as seen in Comparative Example 5.
  • Example 7 In order to remove the oligomers in the oven by increasing the number of times of air ventilation in the heat setting zone, the other film forming conditions were the same as in Example 1 in which intake and exhaust were performed in each chamber of the heat setting zone. As a result, although the cycle was indefinite, the film thickness unevenness was deteriorated. The thickness of the slurry was uneven.
  • the biaxially oriented polyester film of the present invention is excellent in planar properties in the longitudinal direction, it can be suitably used for mold release applications. Particularly, since the in-plane expansion / contraction behavior is uniformed against the tension at the time of processing, it is particularly suitably used for a mold release application using a green sheet in a multilayer ceramic capacitor as a member.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Laminated Bodies (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

L'invention concerne un film de polyester antiadhésif biorienté caractérisé en ce qu'il présente une largeur de 400 mm ou plus et un écart d'épaisseur σ (σMD) par rapport à une valeur moyenne, déterminé par une mesure continue sur 10 000 m dans le sens machine du film, de 0,15 µm ou moins. Le film de polyester antiadhésif peut donner un support moins rigide pour la formation d'une feuille verte et peut réduire les quantités de déformation pendant l'impression sur électrodes. Le film de polyester antiadhésif est optimal pour des applications de barbotine céramique lors de la formation de feuilles vertes minces.
PCT/JP2019/008899 2018-03-12 2019-03-06 Rouleau de film de polyester antiadhésif biorienté WO2019176692A1 (fr)

Priority Applications (3)

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CN201980018027.4A CN111868148A (zh) 2018-03-12 2019-03-06 脱模用双轴取向聚酯膜卷
JP2019540108A JP7169551B2 (ja) 2018-03-12 2019-03-06 離型用二軸配向ポリエステルフィルムロール
KR1020207027933A KR20200131262A (ko) 2018-03-12 2019-03-06 이형용 2축 배향 폴리에스테르 필름 롤

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
JP2021050297A (ja) * 2019-09-26 2021-04-01 東レ株式会社 ポリエステルフィルムロール

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JP7488248B2 (ja) * 2020-12-31 2024-05-21 コーロン インダストリーズ インク ポリエステル離型フィルム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004148537A (ja) * 2002-10-28 2004-05-27 Toyobo Co Ltd セラミックシート製造用離型フィルム
JP2010167771A (ja) * 2008-12-22 2010-08-05 Toyobo Co Ltd 二軸延伸ポリエチレンテレフタレート系樹脂フィルムおよびその製造方法
JP2014133373A (ja) * 2013-01-11 2014-07-24 Toray Ind Inc 離型用二軸配向ポリエステルフィルムおよびその製造方法
JP2017217901A (ja) * 2016-06-02 2017-12-14 東レ株式会社 離型用二軸配向ポリエステルフィルムおよびその製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3678186B2 (ja) * 2001-08-01 2005-08-03 東洋紡績株式会社 熱収縮性ポリエステル系フィルムロール
JP2004291240A (ja) 2003-03-25 2004-10-21 Mitsubishi Polyester Film Copp 離型フィルム
JP2007287215A (ja) * 2006-04-14 2007-11-01 Toray Ind Inc 磁気記録媒体用支持体および磁気記録媒体
JP5125176B2 (ja) 2007-03-29 2013-01-23 東レ株式会社 偏光板離型フィルム用二軸配向ポリエステルフィルムおよびその製造方法
MY171342A (en) * 2013-06-18 2019-10-09 Toray Industries Biaxially-oriented laminated polyester film for mold release applications
JP6500629B2 (ja) 2015-06-19 2019-04-17 東洋紡株式会社 積層フィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004148537A (ja) * 2002-10-28 2004-05-27 Toyobo Co Ltd セラミックシート製造用離型フィルム
JP2010167771A (ja) * 2008-12-22 2010-08-05 Toyobo Co Ltd 二軸延伸ポリエチレンテレフタレート系樹脂フィルムおよびその製造方法
JP2014133373A (ja) * 2013-01-11 2014-07-24 Toray Ind Inc 離型用二軸配向ポリエステルフィルムおよびその製造方法
JP2017217901A (ja) * 2016-06-02 2017-12-14 東レ株式会社 離型用二軸配向ポリエステルフィルムおよびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021050297A (ja) * 2019-09-26 2021-04-01 東レ株式会社 ポリエステルフィルムロール
JP7388091B2 (ja) 2019-09-26 2023-11-29 東レ株式会社 ポリエステルフィルムロール

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KR20200131262A (ko) 2020-11-23
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CN111868148A (zh) 2020-10-30
TW201945446A (zh) 2019-12-01

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