WO2017150193A1 - 高耐熱性ポリエチレンナフタレートシート - Google Patents

高耐熱性ポリエチレンナフタレートシート Download PDF

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WO2017150193A1
WO2017150193A1 PCT/JP2017/005570 JP2017005570W WO2017150193A1 WO 2017150193 A1 WO2017150193 A1 WO 2017150193A1 JP 2017005570 W JP2017005570 W JP 2017005570W WO 2017150193 A1 WO2017150193 A1 WO 2017150193A1
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Prior art keywords
polyethylene naphthalate
sheet
sample
naphthalate sheet
noc
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PCT/JP2017/005570
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English (en)
French (fr)
Japanese (ja)
Inventor
正道 彦坂
聖香 岡田
良敬 田中
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国立大学法人広島大学
帝人株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a high heat-resistant polyethylene naphthalate sheet (or a high heat-resistant polyethylene naphthalate film). More specifically, the high heat-resistant polyethylene naphthalate sheet (or high heat-resistant polyethylene naphthalate film) according to the present invention is a sheet-like (or film-like) polymer material containing nano-oriented crystals of polyethylene naphthalate. is there.
  • Petroleum-derived polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are polyolefins that are general-purpose plastics. It is known as a high-performance, high-performance plastic that has superior mechanical properties, heat resistance, transparency, and the like. In particular, because PET is inexpensive, it is used in large quantities in various bottles, containers, industrial products, industrial parts, etc. (domestic annual production: about 700,000 tons) and is also famous as a recyclable substance. PBT, PEN, and the like are classified as engineering plastics that are high-performance resins.
  • the engineering plastic is defined as a resin having a heat resistant temperature of 100 ° C. or higher, a tensile strength of 50 MPa or higher, and a tensile elastic modulus of 2.5 GPa or higher.
  • engineering plastics having a heat resistant temperature of 150 ° C. or higher are called “super engineering plastics”, and their demand is increasing in fields where higher heat resistance is required, such as electronic equipment.
  • polyester sheets and polyester films obtained by stretching polyester are used.
  • the conventional polyester stretched sheet product and polyester stretched film product are not fully capable of realizing the high performance inherent in polyester.
  • the reason for this is that conventional stretched polyester sheets and stretched films are made of a laminated lamellar structure in which folded chain crystals (FCC) and amorphous are laminated, and have low performance amorphous. It is because it contains 50% or more.
  • a conventional PET uniaxially stretched sheet has a tensile strength ( ⁇ ) at room temperature of 230 MPa and a tensile elastic modulus (E t ) of 2.3 GPa, but a heat resistant temperature (T h ) of about 120 ° C.
  • the melting point (T m ) is 250 to 265 ° C. and the equilibrium melting point (T m 0 ) is 310 ° C., which is extremely lower than the melting point (T m ) of 310 ° C. This is an obstacle to full-scale deployment of PET into industrial products.
  • Patent Documents 1 and 2 and Non-Patent Documents 1 to 3 describe techniques relating to a uniaxially stretched sheet of polyester such as PET.
  • any of the polyester uniaxially stretched sheets described in the above documents has the above-mentioned laminated lamella structure.
  • 4 and 6 of Non-Patent Document 1 show a typical four-point image indicating a laminated lamellar structure from a small-angle X-ray scattering pattern (SAXS pattern) of uniaxially stretched PET.
  • FIG. 8 schematically shows that the uniaxially stretched sheet of PET has a laminated lamellar structure in which amorphous and crystals are laminated.
  • FIG. 5 of Non-Patent Document 3 shows a small-angle X-ray scattering pattern (SAXS pattern) of uniaxially stretched PET, which shows a typical four-point image of a laminated lamella structure.
  • SAXS pattern small-angle X-ray scattering pattern
  • Japanese Patent Publication Japanese Patent Laid-Open No. 7-329170” (published on December 19, 1995) Japanese Patent Publication “Patent No. 3804003 (August 2, 2006)”
  • polyester sheets and polyester films are relatively inexpensive and have excellent mechanical properties, they have insufficient heat resistance, so they can be fully developed into industrial products. Have difficulty.
  • an object of one embodiment of the present invention is to provide a high heat resistance polyethylene naphthalate sheet (high heat resistance polyethylene naphthalate film) by imparting high heat resistance to polyethylene naphthalate among polyesters.
  • the inventors of the present invention conducted nanocrystallization of polyethylene naphthalate by performing crystallization while stretching a melt of polyethylene naphthalate at a rate equal to or higher than the critical elongation strain rate.
  • a polyethylene naphthalate sheet containing nano-oriented crystals of polyethylene naphthalate has a higher heat resistance temperature (T h ⁇ 309 ° C.) and a higher melting point (T m ⁇ 309 ° C.) than a conventional uniaxially stretched sheet.
  • the present invention was completed (another example of polyethylene naphthalate has a high heat resistance temperature (T h ⁇ 291 ° C.) and a high melting point (T m ⁇ 306 ° C.). )
  • the polyethylene naphthalate sheet according to one embodiment of the present invention is a polyethylene naphthalate sheet containing polyethylene naphthalate crystals
  • the crystal is a nano-oriented crystal including a polyethylene naphthalate crystal (also referred to as nano crysatl, NC) in which polymer molecular chains are oriented and the crystal size is 50 nm or less.
  • NC polyethylene naphthalate crystal
  • the heat resistant temperature is 280 ° C. or higher.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention may have a melting point of 285 ° C. or higher.
  • the nano-oriented crystal may have a structure in which spindle-shaped crystals are connected in a bead shape.
  • the nano-oriented crystal may be monoclinic.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention may be a polyethylene naphthalate sheet used for high-temperature processing.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention may be a polyethylene naphthalate sheet used as a base material of a laminate with a transparent conductive layer.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention may be a polyethylene naphthalate sheet used as a base material for a flexible circuit board.
  • one embodiment of the present invention may be a flexible circuit board based on the polyethylene naphthalate sheet according to one embodiment of the present invention.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention has higher heat resistance and a higher melting point than conventional polyethylene naphthalate sheets. Therefore, according to the present invention, the polyethylene naphthalate sheet, which has been difficult to be used as a super engineering plastic due to insufficient heat resistance, can be used for industrial products requiring heat resistance. Can be.
  • (A) And (b) is a figure showing the polarization microscope image (observation result from the through direction) of the sample which concerns on an Example. It is a figure showing the small angle X-ray-scattering image of the sample which concerns on an Example, (a) is the observation result from the through direction, (b) is the observation result from the edge direction, (c) is the observation result from the end direction. Show. It is a figure showing the wide-angle X-ray-scattering image of the sample which concerns on an Example, (a) is the observation result from the through direction, (b) is the observation result from the edge direction, (c) is the observation result from the end direction. Show.
  • a * , B *, and C * (shown in bold in the drawing, the same applies throughout this specification) are NOC reciprocal lattice vectors, and ⁇ * NC is an angle formed by A * and C * .
  • Unique axis is B * // TD.
  • ⁇ is an angle formed by C * and MD
  • ⁇ is an angle formed by A * and ND
  • the clockwise direction is positive.
  • It is a schematic diagram which shows the three-dimensional (3D) form model of NOC, and the size of NC.
  • A, B, and C (shown in bold in the drawing, the same applies throughout this specification) are NOC monoclinic lattice vectors corresponding to the NC size
  • Polyethylene naphthalate sheet of the present invention relates to a polyethylene naphthalate sheet comprising polyethylene naphthalate crystals having a high heat resistance and a high melting point.
  • the “polyethylene naphthalate sheet” means not only a sheet-like polyethylene naphthalate having an average thickness of 0.15 mm or more but also a film-like polyethylene naphthalate having an average thickness of less than 0.15 mm.
  • the said average thickness is not restrict
  • a specific average thickness is preferably in the range of 1 ⁇ m to 10 mm, more preferably in the range of 2 ⁇ m to 5 mm, and particularly preferably in the range of 3 ⁇ m to 1 mm.
  • the “thickness” means a distance between one surface of the polymer sheet and the other surface measured under a certain static load.
  • the “average thickness” means an average value of the maximum value and the minimum value of the thickness of the polymer sheet.
  • the thickness of the polymer sheet can be measured by using a micrometer or by using a scale calibrated with an optical stereomicroscope (Olympus, SZX10-3141) and an objective micrometer.
  • polyethylene naphthalate means a polycondensate of 2,6-naphthalenedicarboxylic acid and ethylene glycol.
  • the polyethylene naphthalate in the present invention is obtained by, for example, transesterifying dimethyl 2,6-naphthalenedicarboxylate with ethylene glycol to obtain a monomer bishydroxyethylene-2,6-naphthalate, and then polycondensing the monomer. It can produce by making it react.
  • the polyethylene naphthalate in the present invention may be not only a homopolymer but also a copolymer.
  • the polyethylene naphthalate sheet of the present invention includes a nano-oriented crystal (NOC) of polyethylene naphthalate.
  • NOC nano-oriented crystal
  • the polyethylene naphthalate sheet of the present invention can be produced, for example, by rolling and stretching a melted polyethylene naphthalate to crystallize (solidify).
  • the polyethylene naphthalate sheet of the present invention has a high heat resistance temperature.
  • heat-resistant temperature means a heat-resistant temperature measured by a test piece size direct reading method using an optical microscope.
  • the above-mentioned “test piece size direct reading method” is an optical microscope with a CCD camera (OLYMPUS, BX51N-33P-OC), a hot stage (Linkam, L-600A), and an image that can quantify the size on the screen.
  • the analysis software Media Cybernetics, Image-Pro PLUS
  • the test piece was 0.7 mm long and 0.5 mm wide. The specimen is heated from room temperature to the maximum temperature T max at a heating rate of 1 K / min.
  • the specimen is strained (contracted or expanded) by 3% or more in the vertical direction (MD) or the transverse direction (TD).
  • the temperature at that time was defined as the heat resistant temperature. That is, the temperature at which the strain ( ⁇ ) becomes ⁇ > 3% or ⁇ ⁇ 3% was defined as the heat resistant temperature (T h ). However, if no temperature at which
  • > 3% was observed up to the melting point (T m ), T h T m was set.
  • the heat resistant temperature of the polyethylene naphthalate sheet according to one embodiment of the present invention is 280 ° C. or higher (more preferably 290 ° C. or higher, more preferably 300 ° C. or higher). Since the equilibrium melting point of PEN is known to be 312 ° C. (reference: Intern. J. Polymeric Mater., 2001, Vol. 50, pp.335-344), the heat resistance temperature of the polyethylene naphthalate of the present invention Can be said to be higher than the temperature of 32 ° C. lower than the equilibrium melting point of PEN (more preferably 22 ° C. lower than the equilibrium melting point, more preferably 12 ° C. lower than the equilibrium melting point).
  • the heat resistance of the polyethylene naphthalate sheet according to one embodiment of the present invention is significantly higher than that of the conventionally known PEN uniaxially stretched sheet having a heat resistance of 130 ° C. to 180 ° C.
  • the heat-resistant temperature of the sample (PEN sheet) according to the examples described later is 309 ° C., and it cannot be predicted by those skilled in the art that the heat-resistant temperature is significantly higher than the conventionally known uniaxially stretched sheet of PEN. This is a remarkable effect.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention has a high melting point in addition to high heat resistance. That is, the melting point of the polyethylene naphthalate sheet according to one embodiment of the present invention is preferably 285 ° C. or higher (more preferably 290 ° C. or higher, more preferably 300 ° C. or higher). Since the equilibrium melting point of PEN is known to be 312 ° C. (reference: Intern. J. Polymeric Mater., 2001, Vol. 50, pp.335-344), the polyethylene naphthalate according to one embodiment of the present invention is used. It can be said that the melting point of phthalate is 27 ° C.
  • the melting point of the polyethylene naphthalate sheet of the present invention is It is understood that it is significantly higher.
  • the melting point of the sample (PEN sheet) according to an example described later is 309 ° C., and the melting point of the PEN sheet according to one embodiment of the present invention is significantly higher than the melting point of the PEN itself. It can be said that this is a remarkable effect that the contractor cannot predict.
  • the difference between the melting point and the heat resistance temperature is preferably 20K or less, more preferably 15K or less, and more preferably 10K or less. More preferably, it is most preferably 5K or less. If the difference between the melting point and the heat-resistant temperature of the polyethylene naphthalate sheet is within the above range, the heat-resistant temperature is sufficiently high with respect to the melting point, so that the polyethylene naphthalate sheet can be used for industrial products that require heat resistance. could be possible.
  • the heat resistance temperature and the melting point are both 309 ° C., and the difference between the melting temperature and the heat resistance temperature of the conventionally known PEN uniaxially stretched sheet is 100K or more.
  • the difference between the melting point and the heat-resistant temperature of the PEN sheet according to one embodiment of the present invention is remarkably small, which is a remarkable effect that cannot be predicted by those skilled in the art.
  • the polyethylene naphthalate sheet of the present invention includes a nano-oriented crystal (NOC) of polyethylene naphthalate.
  • NOC includes polyethylene naphthalate crystal (also referred to as nanocrystal (NC)) in which the crystal size is 50 nm or less and the polymer chain is oriented in the direction of elongation (machine direction, MD). It is a waste.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention preferably contains NOC as a main component.
  • NOC the NOC of polyethylene naphthalate is 60% or more (preferably 70% or more, more preferably 80% or more, more preferably 90% or more, and further preferably 95%. And the like).
  • the proportion of NOC contained in the polyethylene naphthalate sheet can be calculated by X-ray diffraction (reference: Kiyoka N Okada, et al.Polymer Journal (2010) 42, 464-473 ).
  • the NOC fraction is also referred to as f (NOC). Since NOC is highly oriented and non-NOC is isotropic, the NOC fraction can be calculated from the intensity ratio of X-ray scattering.
  • orientation function f c of the NOC has a 0.9 or higher (more preferably 0.95 or more, more preferably 0.97 or higher).
  • the orientation function f c can be measured by, for example, known wide-angle X-ray scattering method (hereinafter referred to as "WAXS method".). Measurement of orientation function f c by WAXS method, for example, when using an imaging plate (Imaging Plate) as a detector, X-rays scattering intensity analysis software (manufactured by Rigaku Corporation, R-axis display) may be measured by using a .
  • the crystal size of NC contained in NOC contained in the polyethylene naphthalate sheet according to one embodiment of the present invention is 50 nm or less (preferably 40 nm or less, more preferably 30 nm or less, and further preferably 25 nm or less).
  • the crystal size of NC can be determined by a known small angle X-ray scattering method (hereinafter referred to as “SAXS method”).
  • SAXS method small angle X-ray scattering method
  • the lower limit of the crystal size of NC is not particularly limited, but is preferably 3 nm or more (preferably 5 nm or more, more preferably 8 nm or more, and further preferably 10 nm or more) from the viewpoint of the melting point.
  • the size d is obtained from the following Bragg equation.
  • FIG. 5 shows a PEN NOC structural model obtained in the example. It was found that the NOC constituting the polyethylene naphthalate sheet obtained in the example had a structure in which spindle-shaped crystals (NC) were connected in a bead shape along the extension direction (MD).
  • the spindle shape means a shape resembling a spindle, which means a cylindrical shape that is thick in the middle and gradually narrows at both ends.
  • spindle shape can also be expressed as “rugby ball shape”.
  • the NC contained in the NOC and the polymer chain contained in the NC are highly oriented in the MD direction, and in the sheet width direction (Tangential direction: TD) and the sheet thickness direction (Normal direction: ND). It was also found that the sequences were arranged with a weak correlation.
  • This is a characteristic structure of the polyethylene naphthalate sheet according to one embodiment of the present invention.
  • the crystal size of NC constituting NOC contained in a polyethylene naphthalate sheet (sample 1 in Table 2) according to an example described later is about 26 nm in the extension direction (MD) as shown in FIG. It was found to be about 18 nm in the direction (TD) and about 20 nm in the sheet thickness direction (ND).
  • the size of MD, TD, and ND is measured, and the largest size may be set as the crystal size. That is, it can be said that the crystal size of NC shown in FIG. 5 is about 26 nm.
  • the NOC contained in the polyethylene naphthalate sheet according to one embodiment of the present invention preferably has a triclinic (or triclinic) crystal structure (Unit cell structure).
  • the NOC contained in the polyethylene naphthalate sheet according to one embodiment of the present invention has such a crystal structure, which contributes to the high heat resistance of the polyethylene naphthalate sheet according to one embodiment of the present invention. it is conceivable that.
  • the NOC contained in the polyethylene naphthalate sheet according to one embodiment of the present invention preferably has a monoclinic crystal form (Morphology).
  • the NOC contained in the polyethylene naphthalate sheet according to one embodiment of the present invention has such a crystal form, which contributes to the high heat resistance of the polyethylene naphthalate sheet according to one embodiment of the present invention. it is conceivable that.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention has excellent heat resistance, it is suitably used as a polyethylene naphthalate sheet for high-temperature processing that is subjected to high-temperature processing, for example, exceeding 200 ° C. Can be used.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention can be suitably used as a base material on which a transparent conductive layer such as ITO is provided. That is, since heat treatment at a high temperature is necessary to reduce the electrical resistance of the transparent conductive layer, the polyethylene naphthalate sheet according to one embodiment of the present invention is processed at a higher temperature than a conventional polyethylene naphthalate sheet. Is possible.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention can be suitably used as a base material for a flexible circuit board that is used for plating or soldering, for example, solder reflow treatment.
  • a flexible circuit board polyimide has been used so far, and polyester has been studied, but it has only dimensional stability of a level used for a reinforcing plate (reference document: Japanese Patent Application Laid-Open No. 2012-15441, special feature). No. 2010-165986).
  • the high heat-resistant polyethylene naphthalate sheet according to one embodiment of the present invention can be provided with high heat resistance equivalent to polyimide while being polyethylene naphthalate, it can be used only as a reinforcing plate that is not directly connected to solder. In addition, it can be used for the substrate itself that contacts the solder.
  • a polyethylene naphthalate sheet having a heat resistant temperature of 280 ° C. or higher is referred to as a “high heat resistant polyethylene naphthalate sheet”.
  • the manufacturing method of the polyethylene naphthalate sheet of the present invention is not particularly limited, and for example, it can be manufactured as follows.
  • the following production method is a method of rolling and stretching a melted polyethylene naphthalate to crystallize (solidify), and a method of rolling and stretching a solidified polyethylene naphthalate sheet to produce a stretched sheet. Is a completely different method.
  • FIG. 11 shows a schematic view of an apparatus (roll rolling elongation crystallization apparatus 10) for producing the polyethylene naphthalate sheet of the present invention.
  • the roll rolling elongation crystallization apparatus 10 includes a supercooled melt feeder (an extruder 2a for melting polyethylene naphthalate and supplying a melt of polyethylene naphthalate, and cooling the melt from the extruder 2a to a supercooled state. And a clamping roll 3.
  • a slit die (not shown) is provided at the discharge port of the extruder 2a, and the shape of the tip of the slit die is square.
  • the polyethylene naphthalate melt discharged from the slit die is cooled until it becomes supercooled when passing through the cooling adapter 2b (the supercooled melt is referred to as “supercooled melt”).
  • the melt is discharged toward the sandwiching roll 3.
  • the difference between the equilibrium melting point (312 ° C. in the case of PEN) and the crystallization temperature is defined as “supercooling degree ⁇ T”, the optimum supercooling degree is particularly limited because it varies significantly depending on the type and characterization of the polymer.
  • ⁇ T 25 ° C. to 100 ° C. (more preferably 40 ° C. to 90 ° C., further preferably 50 ° C. to 85 ° C., most preferably 55 ° C. to 85 ° C.) is preferable.
  • the sandwiching roll 3 is provided so that a pair of rotatable rolls face each other, sandwiching the supercooled melt 1 supplied from the supercooled melt supply machine, and extending in the rotation direction of the roll, into a sheet shape It can be molded.
  • supercooled melt 1 is supplied from a supercooled melt feeder, and sandwiched between sandwiching rolls 3 and rolled at a stretch strain rate equal to or higher than the critical stretch strain rate. By doing so, it may be crystallized. By doing so, the supercooled melt 1 becomes an oriented melt, which can be crystallized while maintaining that state, and the molecular chains contained in the oriented melt are associated with each other without the aid of foreign matter.
  • Generation referred to as “homogeneous nucleation”
  • growth generate NOC, and a polyethylene naphthalate sheet according to one embodiment of the present invention can be manufactured.
  • seat which concerns on 1 aspect of this invention is further demonstrated using the roll rolling elongation crystallization apparatus 10 shown in FIG.
  • FIG. 11 attention is focused on a region from the rolling elongation start (A) by the sandwiching roll 3 to the rolling elongation end (B) (hereinafter referred to as “region AB”).
  • the radius of the pinching roll 3 of the roll rolling elongation crystallization apparatus 10 is R
  • the angular velocity ⁇ of the pinching roll 3 the angle of rotation of the pinching roll 3 is ⁇
  • the thickness of the supercooled melt 1 at any location in the region AB is L 0.
  • the thickness of the polyethylene naphthalate sheet at point B after the end of rolling elongation is L
  • the sheet take-up speed in the pinching roll is V
  • the elongation strain rate is ⁇ .
  • the roll rotation angle ⁇ in the region AB is very small. ⁇ ⁇ 1 (rad) (1)
  • the roll radius R is much larger than the sheet thickness L 0 or L.
  • R >> L 0 , L (2)
  • the center of the minute volume is considered as the origin.
  • the direction (MD) in which the supercooled melt 1 and the polyethylene naphthalate sheet move is the x axis
  • the width direction (TD) of the supercooled melt sheet is the y axis
  • the thickness direction of the supercooled melt sheet is the z axis.
  • the elongation strain rate to be obtained ⁇ xx ⁇ 2 ⁇ ⁇ (R / L 0 ) ⁇ (1 ⁇ L / L 0 ) ⁇ (9) Is obtained.
  • ⁇ xx is a function of L 0 from the equation (9).
  • the maximum elongation strain rate is written as ⁇ max .
  • equation (11) is defined as the elongation strain rate ⁇ ,
  • the radius R of the sandwiching roll 3 and the average thickness L of the polymer sheet after stretching are set so that the stretching strain rate ⁇ (R, L, V) is equal to or higher than the critical stretching strain rate.
  • the critical elongation strain rate ⁇ * (R, L, V) may be a rate determined by any method. For example, it is calculated using the following approximate expression (formula i). There may be. (Formula i)
  • the sheet take-off speed V * at the critical point is determined by supplying a supercooled polyethylene naphthalate melt and sandwiching the polyethylene naphthalate melt between a pair of holding rolls 3 having a radius R.
  • the sheet take-off speed V is a critical point at which NOC is produced when crystallization into a polyethylene naphthalate sheet having a thickness L is performed by rolling and elongation.
  • the critical elongation strain rate ⁇ * (R, L, V) is calculated using the following approximate expression (formula ii). May be. (Formula ii)
  • the thickness L * of the polyethylene naphthalate sheet at the critical point is determined by supplying a supercooled polyethylene naphthalate melt and sandwiching the polyethylene naphthalate melt between a pair of sandwiching rolls 3 having a radius R. It is the thickness L of the polyethylene naphthalate sheet at the critical point where NOC is generated when it is crystallized into a polyethylene naphthalate sheet having a thickness L by rolling and stretching at the sheet take-up speed V.
  • the elongation strain rate ⁇ (R, L, V) at which the NOC fraction becomes 0.6 is changed to the critical elongation strain rate ⁇ * (R, L, V) (reference: Kiyoka N Okada, et al. Polymer Journal (2010) 42, 464-473).
  • NOC is not particularly limited, but can be determined by, for example, an X-ray diffraction method described in Examples described later.
  • the fluidity of the polyethylene naphthalate melt is such that it can be stretched at a critical elongation strain rate or higher (melt flow).
  • the rate is preferably adjusted to Melt ⁇ flow rate (MFR). That is, it can be said that the method for producing a polyethylene naphthalate sheet according to one embodiment of the present invention preferably includes a step of adjusting the fluidity of the polyethylene naphthalate melt.
  • the fluidity of the polyethylene naphthalate melt should be adjusted to such a fluidity that it can be stretched at a critical elongation strain rate or higher.
  • the MFR of the polyethylene naphthalate melt at 300 ° C. is preferably 80 (g / 10 min) or less, more preferably 60 (g / 10 min) or less, and 40 (g / 10 min) or less. More preferably, it is most preferable that it is 20 (g / 10min) or less.
  • the lower limit of the MFR of the polyethylene naphthalate melt at 300 ° C. is not particularly limited as long as it can be extended at a critical elongation strain rate or higher, but usually 3 (g / 10 min) or higher. It is preferable that
  • M n represents a number average molecular weight
  • M w represents a weight average molecular weight
  • M w / M n represents a dispersion index.
  • M n, M w, M w / M n of the PEN was measured using the Tosoh HLC-8320GPC.
  • TSK-gel GMHHR-M ⁇ 2 was used at 40 ° C.
  • a 1: 1 mixed solvent of chloroform and HFIP hexafluoroisopropyl alcohol
  • MFR [300 ° C.] in Table 1 represents the melt flow rate (Melt flow rate, MFR) at 300 ° C. MFR heats and presses a certain amount of synthetic resin in a cylindrical container heated by a heater at a specified temperature (300 ° C) and extrudes it every 10 minutes from an opening (nozzle) provided at the bottom of the container. Measure the amount of resin formed. The value is expressed in units (g / 10 min).
  • the test machine uses an extrusion plastometer specified in JIS K6760, and the measuring method is specified in JIS K7210.
  • PEN elongation crystallization shown in Table 1 was performed.
  • the conditions for elongation crystallization are as shown in Table 2.
  • Table 2 shows the results of elongation crystallization of PEN.
  • MFR the higher the melt fluidity (that is, the lower the viscosity)
  • the fluidity is lowered to some extent (for example, MFR [300 ° C.] is 80 (g / 10 min) or less).
  • a PEN sheet was prepared by using the PEN shown in Table 1 using an extrusion molding machine (manufactured by TOYO SEIKI, Labo Plast Mill). Extrusion conditions were such that the resin was melted at a set temperature of 300 ° C., extruded from a die into a sheet, and placed on a cast roll set at a temperature of 80 ° C. to solidify the sheet.
  • the PEN sheet obtained above was stretched using a stretching machine (manufactured by TOYO SEIKI, batch stretching machine) to prepare a PEN uniaxially stretched sheet. Stretching was performed by stretching the PEN sheet so that the stretching ratio was 5 times in the MD direction at an atmospheric temperature of 150 ° C.
  • the PEN uniaxially stretched sheet obtained above was fixed to a metal frame and fixed at 200 ° C. for 1 minute to prepare a sample (thickness: 0.055 mm) according to a comparative example (this sample is referred to below as (“Sample according to comparative example").
  • FIG. 1 shows the result of observation with a polarizing microscope.
  • FIGS. 1A and 1B show polarization microscope images of Sample 2 in Table 2 as representative examples of samples according to Examples.
  • 1A is a polarization microscope image when the MD is placed parallel to the sensitive color detection plate
  • FIG. 1B is a polarization microscope image when the extinction angle is set.
  • the X-ray wavelength ⁇ 0.06 nm to 0.15 nm, the camera length 300 mm to 3 m, and the detector And an imaging plate (Imaging Plate) was used at room temperature of 25 ° C. Three directions were observed: a direction perpendicular to MD and TD (through), a direction parallel to TD (edge), and a direction parallel to MD (end). For the through and edge samples, MD was set in the Z-axis direction, for end, TD was set in the Z-axis direction, and the X-ray exposure time was 5 to 180 seconds.
  • the imaging plate was read with a reader manufactured by Rigaku Corporation and reading software (Rigaku Corporation, raxwish, control) to obtain a two-dimensional image.
  • FIG. 2 shows a SAXS image of sample 1 in Table 2 as a representative example of the sample according to the example.
  • 2A shows an observation result from the through direction
  • FIG. 2B shows an observation result from the edge direction
  • FIG. 2C shows an observation result from the end direction.
  • FIG. 2A a two-point image strong against MD and a two-point image weak against TD were orthogonal.
  • the two-point image was tilted by ⁇ and ⁇ from MD and ND, respectively (see FIG. 9 for details).
  • PEN nano-oriented crystals were arranged in a 3D lattice.
  • SAXS PEN nano-oriented crystals
  • the PEN NOC is a “3D paracrystal lattice”.
  • NOC lattice form (crystal form) of PEN is monoclinic, and it is a unique axis (reference: International tables for crystallography, Vol.A, (ed. T. Hahn) Netherlands: Kluwer Academic Publishers , 1996, pp. 106-107) was found to be TD (see FIG. 9 for details).
  • MD was set in the Z-axis direction
  • TD was set in the Z-axis direction
  • the X-ray exposure time was 10 to 180 seconds.
  • the imaging plate was read with a reader manufactured by Rigaku Corporation and reading software (Rigaku Corporation, raxwish, control) to obtain a two-dimensional image.
  • FIG. 3 shows a WAXS image of sample 1 in Table 2 as a representative example of the sample according to the example.
  • 3A shows an observation result from the through direction
  • FIG. 3B shows an observation result from the edge direction
  • FIG. 3C shows an observation result from the end direction.
  • PEN NOC is a triclinic ⁇ form (reference: S. Buchner, D. Wiswe, and HG Zachmann, Polymer, 30, 480 ( 1989)).
  • orientation function f c of study Figure 3 (a) spreadsheet software (WaveMetrics Inc., Igor Pro) by performing analysis gave the orientation function f c of the sample according to the embodiment.
  • a declination ( ⁇ ) -wide angle X-ray scattering intensity (I x ) curve was obtained with background correction.
  • Expression of orientation function: f c (3 ⁇ cos 2 ⁇ > ⁇ 1) / 2
  • f c (3 ⁇ cos 2 ⁇ > ⁇ 1) / 2
  • FIG. 4 is a diagram showing indexing of reflection in the observation result from the edge direction in the SAXS shown in FIG.
  • FIG. 4 shows the monochrome image shown in FIG. 2B as a color image.
  • the crystal size of the sample according to the example (Sample 1 in Table 2) (NC crystal size including DEN interface (reference: Patent No. 5765707)) is about 26 nm in the MD direction, about 18 nm in the TD direction, and ND It was found to be about 20 nm in the direction. Further, it was found that the crystal size (NC crystal size) of the sample according to the example (sample 2 in Table 2) was 26 nm in the MD direction and 18 nm in the TD direction.
  • the sample according to the example was presumed to have a structure as shown in FIG. That is, the NOC contained in the sample according to the example has a structure in which spindles (or rugby ball-like) NCs are connected in a bead shape along the MD, and the polymer chains constituting the NC are in the MD. Highly oriented. NC was also oriented with a weak correlation to TD and ND.
  • samples according to the study example of heat-resistant temperature (samples 1 and 2 in Table 2), and the heat resistance temperature T h of the sample of the comparative example was measured by a test piece size direct-reading method using an optical microscope. Place a test piece (length: 0.7 mm, width: 0.5 mm) in a hot stage (Linkam, L-600A) and heat the hot stage from room temperature to the maximum temperature T max at a heating rate of 1 K / min. did. At this time, observation and recording were performed with an optical microscope with a CCD camera (BX51N-33P-OC manufactured by Olympus Corporation).
  • the warp direction (MD) and weft direction (TD) of the test piece are quantitatively measured and contracted by 3% or more to MD or TD ( or the temperature at which initiated the expansion), and a heat resistance temperature T h. That is, the temperature at which the strain ( ⁇ ) becomes ⁇ > 3% or ⁇ ⁇ 3% was defined as the heat resistant temperature (T h ). However, if no temperature at which
  • > 3% was observed up to the melting point (T m ), T h T m was set.
  • Example 1 and 2 of Table 2 samples according to Example No., and the melting point T m of a sample of the comparative example were also considered in conjunction.
  • the strain ( ⁇ ) did not exceed 3% for both MD and TD up to the melting point (T m ).
  • T h the heat resistant temperature T h and a melting point T m of a sample (Sample 1 in Table 2) according to the example was to be about 309 ° C.. Therefore, it was found that the NOC of the sample according to the example (sample 1 in Table 2) exhibits high heat resistance.
  • the temperature (T h (MD)) when the MD is distorted by 3% or more is about 302 ° C.
  • the temperature when the TD is distorted by 3% or more (T h (TD)). It was found to be about 291 ° C.
  • heat resistance temperature T h of the sample according to Example (Sample 2 in Table 2) was set to be about 291 ° C.
  • the melting point T m of a sample (sample 2 of Table 2) according to the embodiment was about 306 ° C..
  • the temperature (T h (MD)) when distorted by 3% or more in the MD direction was about 172 ° C. Therefore, the heat-resistant temperature of the sample according to the comparative example is about 172 ° C.
  • the melting point T m of a sample of the comparative example was about 277 ° C..
  • the sample according to the example greatly exceeded the sample according to the comparative example with respect to the heat-resistant temperature and the melting point. This can be said to be a remarkable effect produced by the sample according to this example.
  • the difference between the heat-resistant temperature and the melting point T m of a sample of the comparative example is 100K or more
  • the difference between the heat-resistant temperature and the melting point T m of a sample according to Example (Sample 2 in Table 2) are 15K It was about.
  • FIG. 9 3D morphological model of NOC
  • a * , B *, and C * are NOC reciprocal lattice vectors
  • ⁇ * NC is an angle formed by A * and C * (that is, an angle between two point images).
  • Unique axes reference: International tables for crystallography, Vol. A, (ed. T. Hahn) Netherlands: Kluwer Academic Publishers, 1996, pp. 106-107)
  • reciprocal lattice is B * // TD is there.
  • ⁇ is the angle formed by C * and MD of NOC
  • ⁇ is the angle formed by A * and ND of NOC, with clockwise being positive.
  • NC is derived from MD as shown in the schematic diagram of FIG. It was found that they were arranged with a strong correlation in the direction tilted ⁇ , and were arranged with a weak correlation in the direction tilted ⁇ from ND.
  • ⁇ NC which is an angle formed by A and C was calculated.
  • ⁇ NC was calculated using the following equation.
  • the polyethylene naphthalate sheet according to one embodiment of the present invention has higher heat resistance than a conventional polyethylene naphthalate sheet. Therefore, according to the present invention, the polyethylene naphthalate sheet, which has been difficult to be used as a super engineering plastic due to insufficient heat resistance, can be used for industrial products that require heat resistance. could be possible.

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WO2010084750A1 (ja) * 2009-01-23 2010-07-29 国立大学法人広島大学 高分子シートおよびその製造方法
JP2011094059A (ja) * 2009-10-30 2011-05-12 Teijin Dupont Films Japan Ltd 二軸配向ポリエステルフィルムおよびその製造方法
JP2011157442A (ja) * 2010-01-29 2011-08-18 Teijin Dupont Films Japan Ltd 配向ポリエステルフィルムおよびその製造方法
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JP2011094059A (ja) * 2009-10-30 2011-05-12 Teijin Dupont Films Japan Ltd 二軸配向ポリエステルフィルムおよびその製造方法
JP2011157442A (ja) * 2010-01-29 2011-08-18 Teijin Dupont Films Japan Ltd 配向ポリエステルフィルムおよびその製造方法
WO2016035598A1 (ja) * 2014-09-02 2016-03-10 国立大学法人広島大学 高耐熱性ポリエステルシート

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