WO2023238819A1 - Method for producing film - Google Patents

Method for producing film Download PDF

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Publication number
WO2023238819A1
WO2023238819A1 PCT/JP2023/020794 JP2023020794W WO2023238819A1 WO 2023238819 A1 WO2023238819 A1 WO 2023238819A1 JP 2023020794 W JP2023020794 W JP 2023020794W WO 2023238819 A1 WO2023238819 A1 WO 2023238819A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
crystal polyester
film
group
die
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PCT/JP2023/020794
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French (fr)
Japanese (ja)
Inventor
桃波 土佐
新治 大友
昌平 莇
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住友化学株式会社
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Publication of WO2023238819A1 publication Critical patent/WO2023238819A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids

Definitions

  • the present disclosure relates to a method of manufacturing a film.
  • This application claims priority based on Japanese Patent Application No. 2022-092148 filed in Japan on June 7, 2022, the contents of which are incorporated herein.
  • the T-die method, the inflation method, and the like are known as methods for producing films containing liquid crystal polyester.
  • Patent Document 1 describes that during film formation, the temperature of the polymer flow path of the film forming apparatus was controlled at all parts of the T-die to the melting point of the liquid crystal resin composition +10°C. .
  • the present disclosure has been made in order to solve the above-mentioned problems, and aims to provide a method for producing a film that contains liquid crystal polyester and can produce a film with excellent surface smoothness. do.
  • the present disclosure has the following aspects.
  • a method for producing a film which includes extruding a composition containing liquid crystal polyester through a die under the following conditions to form a film.
  • the liquid crystal polyester is The method for producing a film according to (1) or (2) above, which contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1).
  • the liquid crystal polyester (A) is The method for producing a film according to any one of (3) to (5) above, which contains a repeating unit represented by the following formula (A1-1).
  • (A1-1)-O-Ar a1-1 -CO- Ar a1-1 represents a naphthylene group
  • the hydrogen atoms in the group represented by Ar a1-1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group.
  • the above-mentioned ( 6) The method for producing a film according to item 6).
  • (9) Contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1), (A1)-O-Ar a1 -CO- (Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
  • the hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group.
  • FIG. 1 is a schematic diagram showing an example of the configuration of a manufacturing apparatus used in a method of manufacturing a film according to an embodiment of the present disclosure, and an example of a process of manufacturing the film.
  • FIG. 2 is an enlarged view of a die portion of the manufacturing apparatus of FIG. 1;
  • the film of the embodiment contains liquid crystal polyester.
  • a method for producing a film according to an embodiment includes extruding a composition containing liquid crystal polyester through a die under the following conditions to form a film.
  • a composition containing liquid crystal polyester through a die under the following conditions to form a film.
  • FT represents the flow start temperature (° C.) of the liquid crystal polyester.
  • Examples of the molding include molding by an inflation method or a T-die method, and molding by an inflation method is preferable.
  • FIG. 1 is a schematic diagram showing an example of the configuration of a manufacturing apparatus 10 used in the film manufacturing method of the embodiment using the inflation method, and an example of the film manufacturing process.
  • a composition containing liquid crystal polyester is put into the cylinder 111 of the extruder 11 and heated while rotating the screw 112 to obtain a fluid M of the composition.
  • the fluid M is extruded from the die 12, and air is sent inside to inflate the fluid M, thereby obtaining a cylindrical tube film 2.
  • a guide plate 14 is provided in the feeding direction of the tube film 2, and the guide plate 14 guides the tube film 2 to a nip roll 16.
  • the tube film 2 is sandwiched between the nip rolls 16, the air inside the cylinder of the tube film 2 is removed, and the film 1 is obtained.
  • the film 1 is wound up by a winding machine 18.
  • FIG. 2 is an enlarged view of the die 12 portion of the manufacturing apparatus 10 described above.
  • the die 12 includes a die lower portion 121, a die middle portion 122, and a die upper portion 123.
  • the temperature settings for each part of the die can be set independently. In this way, when the die is divided into a plurality of parts and the temperature can be set independently for each part, it is preferable that the set temperature of each part of the die is the same temperature.
  • the set temperature of each part of the die may be different from each other, and when the set temperature of each part of the die is different from each other, the set temperature of the die in this specification refers to the part having a discharge port that discharges the composition. means the set temperature of the die. In the die 12, the set temperature of the die is the set temperature of the die upper part 123.
  • the set temperature for the entire die is the set temperature of the die.
  • the conditions -10 ⁇ FT-die set temperature (°C) ⁇ 30 are satisfied, and the conditions -10 ⁇ FT-die set temperature (°C) ⁇ 15 are satisfied.
  • the conditions -10 ⁇ FT-die set temperature (°C) ⁇ 30 are satisfied, and the conditions -10 ⁇ FT-die set temperature (°C) ⁇ 15 are satisfied.
  • the temperature (°C) of the FT-die is -10 or higher, it is possible to produce a film with excellent surface smoothness.
  • the set temperature (° C.) of the FT-die is 30 or less, liquid crystal polyester can be discharged from the die well.
  • Tr represents the temperature (° C.) at which the viscosity of the composition measured under the following measurement conditions is 1.0 ⁇ 10 4 Pa ⁇ s.
  • the temperature (° C.) of the Tr-die By setting the temperature (° C.) of the Tr-die to -35 or higher, it is possible to produce a film with better surface smoothness. By setting the temperature (° C.) of the Tr-die to 10 or less, the composition can be better discharged from the die.
  • the set temperature of the die has been explained using the die used in the inflation method as an example with reference to FIGS. 1 and 2.
  • the set temperature explained in can be applied.
  • the thickness of the film manufactured by the film manufacturing method of the embodiment may be, for example, 30 ⁇ m or more and 300 ⁇ m or less, 30 ⁇ m or more and 200 ⁇ m or less, or 50 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the film is the average value of the values measured at 9 or more points on a portion 5 mm or more inside the outer periphery of the film. More specifically, it can be measured using a U-shaped steel plate micrometer (for example, PMU150-25MJ (manufactured by Mitutoyo Corporation)).
  • the value of the surface roughness (Ra) of the film manufactured by the film manufacturing method of the embodiment is preferably 1.0 ⁇ m or less, more preferably 0.7 ⁇ m or less.
  • the value of surface roughness (Ra) may be 0.2 ⁇ m or more and 0.7 ⁇ m or less.
  • the value of the surface roughness (Ra) may be 0.2 ⁇ m or more and 0.7 ⁇ m or less, 0.2 ⁇ m or more and 0.6 ⁇ m or less, and 0.2 ⁇ m or more and 0.5 ⁇ m or less.
  • the value of the surface roughness (Ra) may be 0.3 ⁇ m or more and 0.7 ⁇ m or less, 0.3 ⁇ m or more and 0.6 ⁇ m or less, and 0.3 ⁇ m or more and 0.5 ⁇ m or less.
  • the surface roughness (Ra) of the film is determined by measuring the arithmetic mean roughness (Ra) in the film width direction using a surface roughness meter (for example, SE600LK31 (manufactured by Kosaka Laboratory Co., Ltd.)) under the following conditions. shall be.
  • Stylus tip radius 2 ⁇ m
  • Stylus speed 0.5mm/sec
  • Measuring force 0.75mN
  • Measurement length 4mm Cutoff value: 0.8mm
  • liquid crystal polyester The composition used in the film manufacturing method of this embodiment includes liquid crystal polyester.
  • the film produced by the film production method of the embodiment contains liquid crystal polyester.
  • the liquid crystal polyester is a polyester that exhibits liquid crystallinity in a molten state, and preferably melts at a temperature of 450°C or lower.
  • the liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester that uses only an aromatic compound as a raw material monomer.
  • liquid crystal polyester (A) suitably used in the film manufacturing method of this embodiment will be explained.
  • the liquid crystal polyester preferably contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1).
  • the liquid crystal polyester may contain 50% by mass or more of the liquid crystal polyester (A), and may contain 80% by mass or more of the liquid crystal polyester (A), based on the total mass of the liquid crystal polyester, and may consist only of the liquid crystal polyester (A). It's okay.
  • the liquid crystal polyester (A) is It includes a repeating unit represented by the following formula (A1).
  • (A1)-O-Ar a1 -CO- Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
  • the hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group.
  • the phenylene group in Ar a1 is preferably a 1,4-phenylene group.
  • the naphthylene group in Ar a1 is preferably a 2,6-naphthylene group.
  • the biphenylylene group in Ar a1 is preferably a 4,4'-biphenylylene group.
  • the hydrogen atoms in the group represented by Ar a1 are each independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 10 carbon atoms that can be substituted with a hydrogen atom include methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, sec-butyl group, tert-butyl group. group, 1-hexyl group, 2-ethylhexyl group, 1-octyl group, and 1-decyl group.
  • Examples of the aryl group having 6 to 20 carbon atoms which can be substituted with a hydrogen atom include monocyclic aromatic groups such as phenyl group, orthotolyl group, methatolyl group, paratolyl group, 1-naphthyl group, 2- Examples include fused aromatic groups such as naphthyl groups.
  • the number of groups substituting the hydrogen atom is preferably 1. or 2 pieces, more preferably 1 piece.
  • the repeating unit represented by the above formula (A1) is a repeating unit derived from aromatic hydroxycarboxylic acid.
  • aromatic hydroxycarboxylic acids include parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, and 4-hydroxybenzoic acid.
  • the aromatic hydroxycarboxylic acids may be used alone or in combination of two or more types in the production of liquid crystal polyester.
  • the repeating unit represented by the above formula (A1) includes a repeating unit in which Ar a1 is a 1,4-phenylene group (for example, a repeating unit derived from 4-hydroxybenzoic acid), and a repeating unit in which Ar a1 is a 2,6- Those that are naphthylene groups (eg, repeating units derived from 2-hydroxy-6-naphthoic acid) are preferred.
  • oil means that the chemical structure changes due to polymerization of the raw material monomer, and no other structural changes occur.
  • each repeating unit may be a repeating unit derived from an acylated aromatic hydroxycarboxylic acid.
  • the number of repeating units represented by the formula (A1) is more than 40%, more than 50%, more than 50%, 60% or more, 60% or more, 70% or more, 70% or more, 80% or more, 80% or more, 85% or more, 85% or more, 90% or more, 90% or more, 95% or more, 95% or more, or 98 % or more, and may consist only of repeating units represented by the formula (A1) (that is, the number of repeating units represented by the formula (A1) may be 100%).
  • the repeating unit represented by the formula (A1) is It is preferable to contain a repeating unit represented by the following formula (A1-1).
  • (A1-1)-O-Ar a1-1 -CO- Ar a1-1 represents a naphthylene group
  • the hydrogen atoms in the group represented by Ar a1-1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group.
  • the number of repeating units represented by the above formula (A1-1) is more than 40% and 90% or less, and 65% of the total number (100%) of repeating units corresponding to the above formula (A1). It is more preferably 80% or less, and even more preferably 70% or more and 75% or less.
  • the viscosity will increase due to the temperature drop during the process of stretching the film and cooling the composition. is moderately suppressed, so a film with excellent surface smoothness can be easily obtained.
  • the liquid crystal polyester (A) mentioned above has a repeating unit represented by the above formula (A1), a repeating unit represented by the following formula (A1-1), and a repeating unit represented by the following formula (A1-2). It is preferable to contain a repeating unit represented by the following formula (A1-1), and more preferably only a repeating unit represented by the following formula (A1-2).
  • the hydrogen atoms in the group represented by Ar a1-1 or Ar a1-2 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
  • the naphthylene group in Ar a1-1 is preferably a 2,6-naphthylene group.
  • the phenylene group in Ar a1-2 is preferably a 1,4-phenylene group.
  • Examples of the halogen atom, alkyl group, or aryl group in Ar a1-1 and Ar a1-2 include those exemplified for Ar a1 above.
  • the liquid crystal polyester (A) mentioned above consists only of repeating units represented by the above formula (A1), and the repeating units represented by the above formula (A1) are represented by the following formula (A1-3). It is preferable to include a repeating unit represented by the following formula (A1-4), and a repeating unit represented by the following formula (A1-3), and a repeating unit represented by the following formula (A1-4). More preferably, it consists only of repeating units. (A1-3)-O-Ar a1-3 -CO- (A1-4)-O-Ar a1-4 -CO- (Ar a1-3 represents a 2,6-naphthylene group, Ar a1-4 represents a 1,4-phenylene group.
  • the hydrogen atoms in the group represented by Ar a1-3 or Ar a1-4 are each independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Good too. )
  • the liquid crystal polyester (A ) for example, for the total number (100%) of all repeating units constituting
  • the number of repeating units represented by the formula (A1-1) is more than 40% and not more than 90%
  • the number of repeating units represented by the formula (A1-2) may be 10% or more and less than 60%
  • the number of repeating units represented by the formula (A1-1) is 65% or more and 80% or less
  • the number of repeating units represented by the formula (A1-2) may be 20% or more and 35% or less
  • the number of repeating units represented by the formula (A1-1) is 70% or more and 75% or less
  • the number of repeating units represented by the formula (A1-2) may be 25% or more and 30% or less.
  • the liquid crystal polyester (A ) for example, for the total number (100%) of all repeating units constituting
  • the number of repeating units represented by the formula (A1-3) is more than 40% and less than 90%
  • the number of repeating units represented by the formula (A1-4) may be 10% or more and less than 60%
  • the number of repeating units represented by the formula (A1-3) is 65% or more and 80% or less
  • the number of repeating units represented by the formula (A1-4) may be 20% or more and 35% or less
  • the number of repeating units represented by the formula (A1-3) is 70% or more and 75% or less
  • the number of repeating units represented by the formula (A1-4) may be 25% or more and 30% or less.
  • the liquid crystal polyester (A) may each independently have two or more types of repeating units represented by the formula (A1).
  • the liquid crystal polyester may have repeating units other than the repeating unit represented by the formula (A1), but the content thereof is determined by the total number of all repeating units constituting the liquid crystal polyester (A) (100 %), preferably 10% or less, more preferably 5% or less.
  • the number of each repeating unit means a value determined by the analysis method described in JP-A-2000-19168. Specifically, a liquid crystal polyester resin is reacted with an alcohol having 1 to 3 carbon atoms in a supercritical state to depolymerize the liquid crystal polyester resin to a monomer that induces its repeating unit, and each of the depolymerized products obtained is The number of each repeating unit can be calculated by quantifying the monomer that induces the repeating unit by liquid chromatography.
  • the flow start temperature of the liquid crystal polyester is preferably 260°C or higher, more preferably 260°C or higher and 400°C or lower, more preferably 260°C or higher and 380°C or lower, more preferably 260°C or higher and 320°C or lower, and 280°C or higher and 310°C or lower. is even more preferable.
  • the flow start temperature is determined by melting the liquid crystal polyester using a flow tester while increasing the temperature at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm 2 ), and extruding it from a nozzle with an inner diameter of 1 mm and a length of 10 mm. Sometimes, it means the temperature at which the liquid crystal polyester exhibits a viscosity of 4800 Pa ⁇ s (48000 poise).
  • the liquid crystal polyester is preferably produced by melt polymerizing raw material monomers corresponding to the repeating units constituting the polyester and, if necessary, solid-phase polymerizing the obtained polymer. Melt polymerization may be carried out in the presence of a catalyst.
  • composition containing liquid crystal polyester preferably contains 80 mass % or more, more preferably 90 mass % or more, and 100 mass % of liquid crystal polyester based on 100 mass % of the total mass of the composition. It is even more preferable.
  • the composition may further contain optional components other than the above-mentioned liquid crystal polyester.
  • Optional ingredients include fillers, resins other than liquid crystal polyester, flame retardants, conductivity imparting materials, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and color prevention agents.
  • agent heat stabilizer, mold release agent, antistatic agent, plasticizer, lubricant, dye, foaming agent, antifoaming agent, viscosity modifier, surfactant, etc.
  • the shape of the composition may be, for example, powder or pellet.
  • Preferred values for the flow start temperature of the composition include the values exemplified as the flow start temperature of the liquid crystal polyester.
  • FT-Tr difference between the FT temperature (°C) and the Tr temperature (°C)
  • the value of FT-Tr (°C) may be 15°C or more and 30°C or less, and may be 18°C or more and 26°C or less.
  • the film manufacturing method of the present embodiment it is effective not to set the die temperature high from the viewpoint of improving the surface smoothness of the surface of the manufactured film. This is because if the set temperature of the die is higher than FT or Tr, the viscosity of the liquid crystal polyester when discharged from the die decreases, and the tension of the film during the manufacturing process is insufficient, resulting in poor surface smoothness of the film. This is thought to be because it becomes a factor that reduces the
  • the film of the embodiment contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1), (A1)-O-Ar a1 -CO- (Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
  • the hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group.
  • the value of surface roughness (Ra) is 1.0 ⁇ m or less.
  • the film of the embodiment can be manufactured from a composition containing liquid crystal polyester (A), it has excellent surface smoothness defined by surface roughness Ra.
  • the value of the surface roughness (Ra) of the film of the embodiment is 1.0 ⁇ m or less, may be 0.7 ⁇ m or less, and may be 0.2 ⁇ m or more and 0.7 ⁇ m or less.
  • the value of surface roughness (Ra) may be 0.2 ⁇ m or more and 0.6 ⁇ m or less, 0.2 ⁇ m or more and 0.5 ⁇ m or less, 0.3 ⁇ m or more and 0.7 ⁇ m or less, and 0. It may be .3 ⁇ m or more and 0.6 ⁇ m or less, and may be 0.3 ⁇ m or more and 0.5 ⁇ m or less.
  • the surface roughness (Ra) value of at least one side of the film is 1.0 ⁇ m or less, may be 0.7 ⁇ m or less, and may be 0.2 ⁇ m or more and 0.6 ⁇ m or less, It may be 0.2 ⁇ m or more and 0.5 ⁇ m or less, 0.3 ⁇ m or more and 0.7 ⁇ m or less, 0.3 ⁇ m or more and 0.6 ⁇ m or less, and 0.3 ⁇ m or more and 0.5 ⁇ m or less. good.
  • the surface roughness (Ra) value of the film on both sides may be 1.0 ⁇ m or less, 0.7 ⁇ m or less, or 0.2 ⁇ m or more and 0.7 ⁇ m or less.
  • ⁇ m or more and 0.6 ⁇ m or less may be 0.2 ⁇ m or more and 0.6 ⁇ m or less, 0.2 ⁇ m or more and 0.5 ⁇ m or less, 0.3 ⁇ m or more and 0.7 ⁇ m or less, and 0.3 ⁇ m or more and 0.6 ⁇ m or less. It may be 0.3 ⁇ m or more and 0.5 ⁇ m or less.
  • liquid crystal polyester in the liquid crystal polyester film examples include those exemplified in the film manufacturing method of the above embodiment.
  • the liquid crystal polyester contained in the film of the embodiment may consist only of liquid crystal polyester (A).
  • the number of repeating units represented by the formula (A1) is 40% or more, more than 40%, 50% or more, Over 50%, over 60%, over 60%, over 70%, over 70%, over 80%, over 80%, over 85%, over 85%, over 90%, over 90%, over 95%, 95% may be more than 98%, or more than 98%, and may consist only of repeating units represented by formula (A1) (i.e., the number of repeating units represented by formula (A1) is 100%). ).
  • the liquid crystal polyester (A) consists only of repeating units represented by the above formula (A1), and the repeating units represented by the above formula (A1) are represented by the above formula (A1-3). It is preferable to include a repeating unit represented by the above formula (A1-4), and a repeating unit represented by the above formula (A1-3), and a repeating unit represented by the above formula (A1-4). More preferably, it consists of only repeating units.
  • the film may further contain optional components other than the liquid crystal polyester.
  • optional components include those exemplified in the film manufacturing method of the above embodiment.
  • liquid crystal polyester contained in the liquid crystal polyester and optional components that may be contained as desired include those same as those exemplified in the composition of the film manufacturing method of the above embodiment. .
  • the thickness of the film of the embodiment may be 30 ⁇ m or more and 300 ⁇ m or less, 30 ⁇ m or more and 200 ⁇ m or less, and 50 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the film is the average value of the values measured at 9 or more points on a portion 5 mm or more inside the outer periphery of the film.
  • the film of the embodiment may be manufactured by the method of manufacturing the film of the embodiment described above.
  • a film with excellent surface smoothness can be provided.
  • the film was cut into a length of 150 mm in the longitudinal direction. A total of three lines (straight lines) were drawn at positions 5 mm from both ends of the film in the width direction and at the center. Similarly, a total of three lines (straight lines) were drawn in the length direction at positions 5 mm from both ends and at the center. Using a U-shaped steel plate micrometer (PMU150-25MJ (manufactured by Mitutoyo Co., Ltd.)), the thickness of each location was measured at the nine points where these six lines intersect, and the arithmetic mean value was calculated. It was thick.
  • PMU150-25MJ manufactured by Mitutoyo Co., Ltd.
  • the liquid crystal polyester (b) was granulated using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM-30) at a cylinder temperature of 320° C. to obtain a pellet-shaped liquid crystal polyester (c).
  • the flow start temperature (FT) of the liquid crystal polyester (c) was 290°C.
  • the liquid crystal polyester (c) had a Tr of 268°C.
  • Example 1 A film was manufactured by an inflation method using the pelletized liquid crystal polyester (c) manufactured above as a molding material. Pellets (composition) of liquid crystal polyester (c) were put into the cylinder of a single-screw extruder with a cylinder inner diameter of 20 mm, and kneaded under the conditions of a cylinder temperature of 295° C. and a screw rotation speed of 30 rpm, and a die inner diameter of 20 mm and a die gap of 1. The film of Example 1 was manufactured using an inflation method in which the composition was extruded from a 15 mm annular die with a film fold width of 80 mm.
  • the die described above was composed of three parts, and the temperature could be set independently for each part.
  • the set temperature of each of the three divided die parts, including the annular die part having a discharge port for discharging the above composition, was 275°C.
  • Example 2 In Example 1, each of Examples 2 to 6 was carried out in the same manner as in Example 1, except that the set temperature of the die of the apparatus, the cylinder temperature, the screw rotation speed, and the film folding width were changed as shown in Table 1. A film was produced. The set temperatures of the three divided dies were set to be the same temperature.
  • Table 1 shows the results of measuring each of the above items for the liquid crystal polyester and film.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The present invention relates to a method for producing a film, the method including extruding a composition containing a liquid crystal polyester from a die under the following condition to form a film: −10≤(FT−set temperature (°C) of die)≤30, where FT is the flow start temperature of the liquid crystal polyester (°C). The molding can be performed through an inflation method or a T die method.

Description

フィルムの製造方法Film manufacturing method
　本開示は、フィルムの製造方法に関する。
　本願は、２０２２年６月７日に、日本に出願された特願２０２２－０９２１４８号に基づき優先権を主張し、その内容をここに援用する。 The present disclosure relates to a method of manufacturing a film.
This application claims priority based on Japanese Patent Application No. 2022-092148 filed in Japan on June 7, 2022, the contents of which are incorporated herein.
　液晶ポリエステルを含有するフィルムの製造方法として、Ｔダイ法やインフレーション法などが知られている。 The T-die method, the inflation method, and the like are known as methods for producing films containing liquid crystal polyester.
　例えば、特許文献１には、フィルムの製膜において、製膜装置のポリマー流路はＴダイのすべての部分で温度を液晶性樹脂組成物の融点＋１０℃に制御されたことが記載されている。 For example, Patent Document 1 describes that during film formation, the temperature of the polymer flow path of the film forming apparatus was controlled at all parts of the T-die to the melting point of the liquid crystal resin composition +10°C. .
特開２００６－２９９２５４号公報Japanese Patent Application Publication No. 2006-299254
　しかし、液晶ポリエステルを含有するフィルムの製造方法によって、製造されるフィルムの表面平滑性の向上については、未だ検討の余地がある。 However, there is still room for investigation into improving the surface smoothness of films produced by methods for producing films containing liquid crystalline polyester.
　本開示は、上記のような問題点を解消するためになされたものであり、液晶ポリエステルを含有し、表面平滑性に優れたフィルムを製造可能な、フィルムの製造方法を提供することを目的とする。 The present disclosure has been made in order to solve the above-mentioned problems, and aims to provide a method for producing a film that contains liquid crystal polyester and can produce a film with excellent surface smoothness. do.
　本開示は以下の態様を有する。 The present disclosure has the following aspects.
（１）　液晶ポリエステルを含む組成物を、以下の条件でダイから押し出して、フィルムを成形することを含む、フィルムの製造方法。
　－１０≦ＦＴ－前記ダイの設定温度（℃）≦３０
　ＦＴ：前記液晶ポリエステルの流動開始温度（℃）
（２）　前記ダイの設定温度がさらに以下の条件を満たす、前記（１）に記載のフィルムの製造方法。
　－３５≦Ｔｒ－前記ダイの設定温度（℃）≦１０
　Ｔｒ：前記組成物の下記測定条件で測定された粘度が１．０×１０４Ｐａ・ｓとなる温度（℃）
　測定条件：
　装置：回転式レオメータ
　降温速度：５℃／ｍｉｎ
　ひずみ：０．０５％
　周波数：１Ｈｚ
（３）　前記液晶ポリエステルは、
　下記式（Ａ１）で表される繰返し単位を含む液晶ポリエステル（Ａ）を含有する、前記（１）又は（２）に記載のフィルムの製造方法。
　（Ａ１）－Ｏ－Ａｒａ１－ＣＯ－
（Ａｒａ１は、フェニレン基、ナフチレン基又はビフェニリレン基を表し、
　Ａｒａ１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）
（４）　前記液晶ポリエステル（Ａ）を構成する全繰返し単位の合計数（１００％）に対して、前記式（Ａ１）で表される繰返し単位の数が４０％超である、前記（３）に記載のフィルムの製造方法。
（５）　前記液晶ポリエステル（Ａ）が、前記式（Ａ１）で表される繰返し単位のみからなる、前記（３）又は（４）に記載のフィルムの製造方法。
（６）　前記液晶ポリエステル（Ａ）は、
　下記式（Ａ１－１）で表される繰返し単位を含む、前記（３）～（５）のいずれか一つに記載のフィルムの製造方法。
　（Ａ１－１）－Ｏ－Ａｒａ１－１－ＣＯ－
（Ａｒａ１－１は、ナフチレン基を表し、
　Ａｒａ１－１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）
（７）　前記式（Ａ１）に該当する繰返し単位の合計数（１００％）に対し、前記式（Ａ１－１）で表される繰返し単位の数が４０％超９０％以下である、前記（６）に記載のフィルムの製造方法。
（８）　前記成形が、インフレーション法又はＴダイ法による成形である、前記（１）～（７）のいずれか一つに記載のフィルムの製造方法。
（９）　下記式（Ａ１）で表される繰返し単位を含む液晶ポリエステル（Ａ）を含有し、　（Ａ１）－Ｏ－Ａｒａ１－ＣＯ－
（Ａｒａ１は、フェニレン基、ナフチレン基又はビフェニリレン基を表し、
　Ａｒａ１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）
　表面粗さ（Ｒａ）の値が１．０μｍ以下である、フィルム。 (1) A method for producing a film, which includes extruding a composition containing liquid crystal polyester through a die under the following conditions to form a film.
-10≦FT-Set temperature of the die (℃)≦30
FT: Flow start temperature of the liquid crystal polyester (°C)
(2) The method for producing a film according to (1) above, wherein the temperature setting of the die further satisfies the following conditions.
-35≦Tr-Set temperature of the die (°C)≦10
Tr: Temperature (°C) at which the viscosity of the composition measured under the following measurement conditions is 1.0 × 10 4 Pa・s
Measurement condition:
Equipment: Rotary rheometer Cooling rate: 5℃/min
Strain: 0.05%
Frequency: 1Hz
(3) The liquid crystal polyester is
The method for producing a film according to (1) or (2) above, which contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1).
(A1)-O-Ar a1 -CO-
(Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
The hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
(4) The above (3), wherein the number of repeating units represented by the formula (A1) is more than 40% with respect to the total number (100%) of all repeating units constituting the liquid crystal polyester (A). The method for producing the film described in .
(5) The method for producing a film according to (3) or (4) above, wherein the liquid crystal polyester (A) consists only of repeating units represented by the formula (A1).
(6) The liquid crystal polyester (A) is
The method for producing a film according to any one of (3) to (5) above, which contains a repeating unit represented by the following formula (A1-1).
(A1-1)-O-Ar a1-1 -CO-
(Ar a1-1 represents a naphthylene group,
The hydrogen atoms in the group represented by Ar a1-1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
(7) The above-mentioned ( 6) The method for producing a film according to item 6).
(8) The method for producing a film according to any one of (1) to (7) above, wherein the molding is performed by an inflation method or a T-die method.
(9) Contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1), (A1)-O-Ar a1 -CO-
(Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
The hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
A film having a surface roughness (Ra) of 1.0 μm or less.
　液晶ポリエステルを含有し、表面平滑性に優れたフィルムを製造可能な、フィルムの製造方法を提供できる。 It is possible to provide a method for producing a film that contains liquid crystal polyester and can produce a film with excellent surface smoothness.
本開示の一実施形態のフィルムの製造方法に用いられる製造装置の構成の一例、及びフィルムの製造過程の一例を示す模式図である。FIG. 1 is a schematic diagram showing an example of the configuration of a manufacturing apparatus used in a method of manufacturing a film according to an embodiment of the present disclosure, and an example of a process of manufacturing the film. 図１の製造装置のダイの部分の拡大図である。FIG. 2 is an enlarged view of a die portion of the manufacturing apparatus of FIG. 1;
　以下、本開示のフィルムの製造方法、及びフィルムの実施形態を説明する。実施形態のフィルムは液晶ポリエステルを含有する。 Hereinafter, a method for manufacturing a film of the present disclosure and embodiments of the film will be described. The film of the embodiment contains liquid crystal polyester.
≪フィルムの製造方法≫
　実施形態のフィルムの製造方法は、液晶ポリエステルを含む組成物を、以下の条件でダイから押し出して、フィルムを成形することを含む。
　－１０≦ＦＴ－ダイの設定温度（℃）≦３０
　本明細書において、ＦＴは、前記液晶ポリエステルの流動開始温度（℃）を表す。 ≪Film manufacturing method≫
A method for producing a film according to an embodiment includes extruding a composition containing liquid crystal polyester through a die under the following conditions to form a film.
-10≦FT-Die setting temperature (℃)≦30
In this specification, FT represents the flow start temperature (° C.) of the liquid crystal polyester.
　前記成形としては、インフレーション法又はＴダイ法による成形が挙げられ、インフレーション法による成形であることが好ましい。 Examples of the molding include molding by an inflation method or a T-die method, and molding by an inflation method is preferable.
　以下、実施形態のフィルムの製造方法について、インフレーション法によるフィルムの製造を行う場合を例に説明する。 Hereinafter, the film manufacturing method of the embodiment will be explained using an example in which the film is manufactured by an inflation method.
　図１は、インフレーション法による実施形態のフィルムの製造方法に用いられる製造装置１０の構成の一例、及びフィルムの製造過程の一例を示す模式図である。 FIG. 1 is a schematic diagram showing an example of the configuration of a manufacturing apparatus 10 used in the film manufacturing method of the embodiment using the inflation method, and an example of the film manufacturing process.
　まず、液晶ポリエステルを含む組成物を、押出機１１のシリンダー１１１内へ投入し、スクリュー１１２を回転させながら加熱し、組成物の流動物Ｍを得る。 First, a composition containing liquid crystal polyester is put into the cylinder 111 of the extruder 11 and heated while rotating the screw 112 to obtain a fluid M of the composition.
　次いで、流動物Ｍをダイ１２から押し出し、内部に空気を送り込んで流動物Ｍを膨らませることで、筒状のチューブフィルム２を得る。チューブフィルム２の送り方向にはガイド板１４が設けられており、当該ガイド板１４はチューブフィルム２をニップロール１６へと誘導する。ニップロール１６によってチューブフィルム２が挟みこまれると、チューブフィルム２の筒の内部の空気が抜かれ、フィルム１が得られる。フィルム１は、巻取機１８により巻き取られる。 Next, the fluid M is extruded from the die 12, and air is sent inside to inflate the fluid M, thereby obtaining a cylindrical tube film 2. A guide plate 14 is provided in the feeding direction of the tube film 2, and the guide plate 14 guides the tube film 2 to a nip roll 16. When the tube film 2 is sandwiched between the nip rolls 16, the air inside the cylinder of the tube film 2 is removed, and the film 1 is obtained. The film 1 is wound up by a winding machine 18.
　図２は、上記の製造装置１０のダイ１２の部分の拡大図である。ダイ１２は、ダイ下部１２１、ダイ中部１２２、及びダイ上部１２３の各部分を備える。ダイの各部分の設定温度は、それぞれ独立に設定可能である。
　このように、ダイが複数部分に分割されるなどして、部分ごとに独立に温度設定が可能である場合、ダイの各部分の設定温度は、互いに同一の温度であることが好ましい。ダイの各部分の設定温度は互いに異なる温度であってもよく、ダイの各部分の設定温度が互いに異なる場合、本明細書におけるダイの設定温度とは、組成物を吐出する吐出口を有する部分のダイの設定温度を意味する。ダイ１２においては、ダイの設定温度は、ダイ上部１２３の設定温度である。 FIG. 2 is an enlarged view of the die 12 portion of the manufacturing apparatus 10 described above. The die 12 includes a die lower portion 121, a die middle portion 122, and a die upper portion 123. The temperature settings for each part of the die can be set independently.
In this way, when the die is divided into a plurality of parts and the temperature can be set independently for each part, it is preferable that the set temperature of each part of the die is the same temperature. The set temperature of each part of the die may be different from each other, and when the set temperature of each part of the die is different from each other, the set temperature of the die in this specification refers to the part having a discharge port that discharges the composition. means the set temperature of the die. In the die 12, the set temperature of the die is the set temperature of the die upper part 123.
　なお、ダイが複数部分に分割されていない場合や、部分ごとに独立に温度設定が可能ではない場合には、そのダイの全体に対する設定温度が、ダイの設定温度である。 Note that if the die is not divided into multiple parts or if the temperature cannot be set independently for each part, the set temperature for the entire die is the set temperature of the die.
　実施形態のフィルムの製造方法においては、－１０≦ＦＴ－ダイの設定温度（℃）≦３０の条件を満たし、－１０≦ＦＴ－ダイの設定温度（℃）≦１５の条件が満たされることが好ましい。
　ＦＴ－ダイの設定温度（℃）が、－１０以上であることで、表面平滑性に優れたフィルムを製造可能である。
　ＦＴ－ダイの設定温度（℃）が、３０以下であることで、液晶ポリエステルのダイからの吐出が良好となる。 In the film manufacturing method of the embodiment, the conditions -10≦FT-die set temperature (°C)≦30 are satisfied, and the conditions -10≦FT-die set temperature (°C)≦15 are satisfied. preferable.
By setting the temperature (°C) of the FT-die to -10 or higher, it is possible to produce a film with excellent surface smoothness.
When the set temperature (° C.) of the FT-die is 30 or less, liquid crystal polyester can be discharged from the die well.
　－３５≦Ｔｒ－ダイの設定温度（℃）≦１０の条件が満たされることが好ましく、－３５≦Ｔｒ－ダイの設定温度（℃）≦－５の条件が満たされることがより好ましい。
　本明細書において、Ｔｒは、前記組成物の下記測定条件で測定された粘度が１．０×１０４Ｐａ・ｓとなる温度（℃）を表す。
　測定条件：
　装置：回転式レオメータ
　降温速度：５℃／ｍｉｎ
　ひずみ：０．０５％
　周波数：１Ｈｚ It is preferable that the condition -35≦Tr-die setting temperature (°C)≦10 is satisfied, and it is more preferable that the condition -35≦Tr-die setting temperature (°C)≦-5 is satisfied.
In this specification, Tr represents the temperature (° C.) at which the viscosity of the composition measured under the following measurement conditions is 1.0×10 4 Pa·s.
Measurement condition:
Equipment: Rotary rheometer Cooling rate: 5℃/min
Strain: 0.05%
Frequency: 1Hz
　Ｔｒ－ダイの設定温度（℃）を、－３５以上とすることで、表面平滑性により優れたフィルムを製造可能である。
　Ｔｒ－ダイの設定温度（℃）を、１０以下とすることで、組成物のダイからの吐出がより良好となる。 By setting the temperature (° C.) of the Tr-die to -35 or higher, it is possible to produce a film with better surface smoothness.
By setting the temperature (° C.) of the Tr-die to 10 or less, the composition can be better discharged from the die.
　上記では、図１～２を参照してインフレーション法で用いられるダイを例に、ダイの設定温度を説明したが、Ｔダイ法等の任意の成形に用いられるダイに対しても同様に、上記で説明した設定温度を適用可能である。 In the above, the set temperature of the die has been explained using the die used in the inflation method as an example with reference to FIGS. 1 and 2. The set temperature explained in can be applied.
　実施形態のフィルムの製造方法により製造されるフィルムの厚さは、例えば３０μｍ以上３００μｍ以下であってよく、３０μｍ以上２００μｍ以下であってもよく、５０μｍ以上２００μｍ以下であってもよい。
　フィルムの厚さは、フィルムの外周から５ｍｍ以上内側の部分に対し、９箇所以上計測した値の平均値とする。より具体的には、Ｕ字形鋼板マイクロメータ（例えば、ＰＭＵ１５０－２５ＭＪ（株式会社ミツトヨ製））を用いて計測することができる。 The thickness of the film manufactured by the film manufacturing method of the embodiment may be, for example, 30 μm or more and 300 μm or less, 30 μm or more and 200 μm or less, or 50 μm or more and 200 μm or less.
The thickness of the film is the average value of the values measured at 9 or more points on a portion 5 mm or more inside the outer periphery of the film. More specifically, it can be measured using a U-shaped steel plate micrometer (for example, PMU150-25MJ (manufactured by Mitutoyo Corporation)).
　実施形態のフィルムの製造方法により製造されるフィルムの表面粗さ（Ｒａ）の値は、１．０μｍ以下が好ましく、０．７μｍ以下がより好ましい。表面粗さ（Ｒａ）の値は、０．２μｍ以上０．７μｍ以下であってよい。表面粗さ（Ｒａ）の値は、０．２μｍ以上０．７μｍ以下であってよく、０．２μｍ以上０．６μｍ以下であってよく、０．２μｍ以上０．５μｍ以下であってよい。表面粗さ（Ｒａ）の値は、０．３μｍ以上０．７μｍ以下であってよく、０．３μｍ以上０．６μｍ以下であってよく、０．３μｍ以上０．５μｍ以下であってよい。 The value of the surface roughness (Ra) of the film manufactured by the film manufacturing method of the embodiment is preferably 1.0 μm or less, more preferably 0.7 μm or less. The value of surface roughness (Ra) may be 0.2 μm or more and 0.7 μm or less. The value of the surface roughness (Ra) may be 0.2 μm or more and 0.7 μm or less, 0.2 μm or more and 0.6 μm or less, and 0.2 μm or more and 0.5 μm or less. The value of the surface roughness (Ra) may be 0.3 μm or more and 0.7 μm or less, 0.3 μm or more and 0.6 μm or less, and 0.3 μm or more and 0.5 μm or less.
　フィルムの表面粗さ（Ｒａ）は、以下の条件で、表面粗さ計（例えば、ＳＥ６００ＬＫ３１（株式会社小坂研究所製））を用いてフィルム幅方向の算術平均粗さ（Ｒａ）を測定したものとする。
　触針先端半径：２μｍ
　触針速度　　：０．５ｍｍ／ｓｅｃ
　測定力　　　：０．７５ｍＮ
　測定長　　　：４ｍｍ
　カットオフ値：０．８ｍｍ The surface roughness (Ra) of the film is determined by measuring the arithmetic mean roughness (Ra) in the film width direction using a surface roughness meter (for example, SE600LK31 (manufactured by Kosaka Laboratory Co., Ltd.)) under the following conditions. shall be.
Stylus tip radius: 2μm
Stylus speed: 0.5mm/sec
Measuring force: 0.75mN
Measurement length: 4mm
Cutoff value: 0.8mm
（液晶ポリエステル）
　本実施形態のフィルムの製造方法に用いられる組成物は、液晶ポリエステルを含む。 (liquid crystal polyester)
The composition used in the film manufacturing method of this embodiment includes liquid crystal polyester.
　すなわち、実施形態のフィルムの製造方法により製造されるフィルムは、液晶ポリエステルを含有する。 That is, the film produced by the film production method of the embodiment contains liquid crystal polyester.
　前記液晶ポリエステルは、溶融状態で液晶性を示すポリエステルであり、４５０℃以下の温度で溶融するものであることが好ましい。 The liquid crystal polyester is a polyester that exhibits liquid crystallinity in a molten state, and preferably melts at a temperature of 450°C or lower.
　前記液晶ポリエステルは、芳香族化合物のみを原料モノマーとする全芳香族液晶ポリエステルであることが好ましい。 The liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester that uses only an aromatic compound as a raw material monomer.
　以下、本実施形態のフィルムの製造方法に好適に用いられる液晶ポリエステル（Ａ）について説明する。 Hereinafter, the liquid crystal polyester (A) suitably used in the film manufacturing method of this embodiment will be explained.
　前記液晶ポリエステルは、下記式（Ａ１）で表される繰返し単位を含む液晶ポリエステル（Ａ）を含有することが好ましい。
　前記液晶ポリエステルは、前記液晶ポリエステルの総質量に対して、液晶ポリエステル（Ａ）を５０質量％以上含有してよく、８０質量％以上含有してよく、液晶ポリエステル（Ａ）のみからなるものであってもよい。 The liquid crystal polyester preferably contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1).
The liquid crystal polyester may contain 50% by mass or more of the liquid crystal polyester (A), and may contain 80% by mass or more of the liquid crystal polyester (A), based on the total mass of the liquid crystal polyester, and may consist only of the liquid crystal polyester (A). It's okay.
　前記液晶ポリエステル（Ａ）は、
　下記式（Ａ１）で表される繰返し単位を含む。
　（Ａ１）－Ｏ－Ａｒａ１－ＣＯ－
（Ａｒａ１は、フェニレン基、ナフチレン基又はビフェニリレン基を表し、
　Ａｒａ１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。） The liquid crystal polyester (A) is
It includes a repeating unit represented by the following formula (A1).
(A1)-O-Ar a1 -CO-
(Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
The hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
　前記Ａｒａ１におけるフェニレン基としては１，４－フェニレン基が好ましい。前記Ａｒａ１におけるナフチレン基としては、２，６－ナフチレン基が好ましい。前記Ａｒａ１におけるビフェニリレン基としては、４，４’－ビフェニリレン基が好ましい。 The phenylene group in Ar a1 is preferably a 1,4-phenylene group. The naphthylene group in Ar a1 is preferably a 2,6-naphthylene group. The biphenylylene group in Ar a1 is preferably a 4,4'-biphenylylene group.
　Ａｒａ１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、炭素数１～１０のアルキル基、又は炭素数６～２０のアリール基で置換されていることがより好ましい。 It is more preferable that the hydrogen atoms in the group represented by Ar a1 are each independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
　前記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　水素原子と置換可能な前記炭素数１～１０のアルキル基の例としては、メチル基、エチル基、１－プロピル基、イソプロピル基、１－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、１－ヘキシル基、２－エチルヘキシル基、１－オクチル基及び１－デシル基等が挙げられる。 Examples of the alkyl group having 1 to 10 carbon atoms that can be substituted with a hydrogen atom include methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, sec-butyl group, tert-butyl group. group, 1-hexyl group, 2-ethylhexyl group, 1-octyl group, and 1-decyl group.
　水素原子と置換可能な前記炭素数６～２０のアリール基の例としては、フェニル基、オルトトリル基、メタトリル基、パラトリル基等のような単環式芳香族基や、１－ナフチル基、２－ナフチル基等のような縮環式芳香族基が挙げられる。 Examples of the aryl group having 6 to 20 carbon atoms which can be substituted with a hydrogen atom include monocyclic aromatic groups such as phenyl group, orthotolyl group, methatolyl group, paratolyl group, 1-naphthyl group, 2- Examples include fused aromatic groups such as naphthyl groups.
　Ａｒａ１で表される前記基中の１個以上の水素原子が、前記ハロゲン原子、前記アルキル基又は前記アリール基で置換されている場合、前記水素原子を置換する基の数は、好ましくは１個又は２個であり、より好ましくは１個である。 When one or more hydrogen atoms in the group represented by Ar a1 are substituted with the halogen atom, the alkyl group, or the aryl group, the number of groups substituting the hydrogen atom is preferably 1. or 2 pieces, more preferably 1 piece.
　上記式（Ａ１）で表される繰返し単位は、芳香族ヒドロキシカルボン酸に由来する繰返し単位である。
　前記芳香族ヒドロキシカルボン酸としては、例えば、パラヒドロキシ安息香酸、メタヒドロキシ安息香酸、２－ヒドロキシ－６－ナフトエ酸、２－ヒドロキシ－３－ナフトエ酸、１－ヒドロキシ－５－ナフトエ酸、４－ヒドロキシ－４’－カルボキシジフェニルエーテルや、これらの芳香族ヒドロキシカルボン酸の芳香環にある水素原子の一部が、アルキル基、アリール基及びハロゲン原子からなる群より選ばれる置換基で置換されてなる芳香族ヒドロキシカルボン酸が挙げられる。前記芳香族ヒドロキシカルボン酸は、液晶ポリエステルの製造において、単独で用いてもよく、２種以上を組み合わせて用いてもよい。　上記式（Ａ１）で表される繰返し単位としては、Ａｒａ１が１，４－フェニレン基である繰り返し単位（例えば、４－ヒドロキシ安息香酸に由来する繰返し単位）、及びＡｒａ１が２，６－ナフチレン基であるもの（例えば、２－ヒドロキシ－６－ナフトエ酸に由来する繰返し単位）が好ましい。 The repeating unit represented by the above formula (A1) is a repeating unit derived from aromatic hydroxycarboxylic acid.
Examples of the aromatic hydroxycarboxylic acids include parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, and 4-hydroxybenzoic acid. Hydroxy-4'-carboxydiphenyl ether or an aromatic product in which some of the hydrogen atoms in the aromatic ring of these aromatic hydroxycarboxylic acids are substituted with a substituent selected from the group consisting of an alkyl group, an aryl group, and a halogen atom. and the group hydroxycarboxylic acids. The aromatic hydroxycarboxylic acids may be used alone or in combination of two or more types in the production of liquid crystal polyester. The repeating unit represented by the above formula (A1) includes a repeating unit in which Ar a1 is a 1,4-phenylene group (for example, a repeating unit derived from 4-hydroxybenzoic acid), and a repeating unit in which Ar a1 is a 2,6- Those that are naphthylene groups (eg, repeating units derived from 2-hydroxy-6-naphthoic acid) are preferred.
　本明細書において、「由来」とは、原料モノマーが重合するために化学構造が変化し、その他の構造変化が生じないことを意味する。 As used herein, "origin" means that the chemical structure changes due to polymerization of the raw material monomer, and no other structural changes occur.
　ここでの由来は、当該化合物の重合可能な誘導体を由来とする場合も包含する。例えば、各繰返し単位は、芳香族ヒドロキシカルボン酸のアシル化物に由来する繰返し単位であってよい。 The origin here also includes cases where the origin is a polymerizable derivative of the compound. For example, each repeating unit may be a repeating unit derived from an acylated aromatic hydroxycarboxylic acid.
　液晶ポリエステル（Ａ）において、前記式（Ａ１）で表される繰返し単位の含有割合が多いほど、フィルムが延伸され組成物が冷却される過程での粘度上昇が抑制され、表面平滑性に優れるフィルムが容易に得られる。
　前記液晶ポリエステル（Ａ）を構成する全繰返し単位の合計数（１００％）に対して、前記式（Ａ１）で表される繰返し単位の数は、４０％超、５０％以上、５０％超、６０％以上、６０％超、７０％以上、７０％超、８０％以上、８０％超、８５％以上、８５％超、９０％以上、９０％超、９５％以上、９５％超、又は９８％以上であってよく、前記式（Ａ１）で表される繰返し単位のみからなってよい（すなわち、前記式（Ａ１）で表される繰返し単位の数が１００％であってよい）。 In the liquid crystal polyester (A), the higher the content of the repeating unit represented by the formula (A1), the more suppressed is the increase in viscosity during the process of stretching the film and cooling the composition, resulting in a film with excellent surface smoothness. can be easily obtained.
Relative to the total number (100%) of all repeating units constituting the liquid crystal polyester (A), the number of repeating units represented by the formula (A1) is more than 40%, more than 50%, more than 50%, 60% or more, 60% or more, 70% or more, 70% or more, 80% or more, 80% or more, 85% or more, 85% or more, 90% or more, 90% or more, 95% or more, 95% or more, or 98 % or more, and may consist only of repeating units represented by the formula (A1) (that is, the number of repeating units represented by the formula (A1) may be 100%).
　上記で挙げた液晶ポリエステル（Ａ）としては、
　前記式（Ａ１）で表される繰返し単位が、
　下記式（Ａ１－１）で表される繰返し単位を含むことが好ましい。
　（Ａ１－１）－Ｏ－Ａｒａ１－１－ＣＯ－
（Ａｒａ１－１は、ナフチレン基を表し、
　Ａｒａ１－１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。） As the liquid crystal polyester (A) mentioned above,
The repeating unit represented by the formula (A1) is
It is preferable to contain a repeating unit represented by the following formula (A1-1).
(A1-1)-O-Ar a1-1 -CO-
(Ar a1-1 represents a naphthylene group,
The hydrogen atoms in the group represented by Ar a1-1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
　前記式（Ａ１）に該当する繰返し単位の合計数（１００％）に対し、前記式（Ａ１－１）で表される繰返し単位の数が４０％超９０％以下であることが好ましく、６５％以上８０％以下であることがより好ましく、７０％以上７５％以下であることがさらに好ましい。
　液晶ポリエステル（Ａ）において、前記式（Ａ１－１）で表される繰返し単位の含有割合が上記数値範囲内であると、フィルムが延伸され組成物が冷却される過程での温度降下による粘度上昇が適度に抑制されるため、表面平滑性に優れるフィルムが容易に得られる。 It is preferable that the number of repeating units represented by the above formula (A1-1) is more than 40% and 90% or less, and 65% of the total number (100%) of repeating units corresponding to the above formula (A1). It is more preferably 80% or less, and even more preferably 70% or more and 75% or less.
In the liquid crystal polyester (A), if the content ratio of the repeating unit represented by the formula (A1-1) is within the above numerical range, the viscosity will increase due to the temperature drop during the process of stretching the film and cooling the composition. is moderately suppressed, so a film with excellent surface smoothness can be easily obtained.
　上記で挙げた液晶ポリエステル（Ａ）としては、前記式（Ａ１）で表される繰返し単位が、下記式（Ａ１－１）で表される繰返し単位、及び下記式（Ａ１－２）で表される繰返し単位を含むことが好ましく、下記式（Ａ１－１）で表される繰返し単位、及び下記式（Ａ１－２）で表される繰返し単位のみからなることがより好ましい。
　（Ａ１－１）－Ｏ－Ａｒａ１－１－ＣＯ－
　（Ａ１－２）－Ｏ－Ａｒａ１－２－ＣＯ－
（Ａｒａ１－１は、ナフチレン基を表し、
　Ａｒａ１－２は、フェニレン基を表す。
　Ａｒａ１－１又はＡｒａ１－２で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。） The liquid crystal polyester (A) mentioned above has a repeating unit represented by the above formula (A1), a repeating unit represented by the following formula (A1-1), and a repeating unit represented by the following formula (A1-2). It is preferable to contain a repeating unit represented by the following formula (A1-1), and more preferably only a repeating unit represented by the following formula (A1-2).
(A1-1)-O-Ar a1-1 -CO-
(A1-2)-O-Ar a1-2 -CO-
(Ar a1-1 represents a naphthylene group,
Ar a1-2 represents a phenylene group.
The hydrogen atoms in the group represented by Ar a1-1 or Ar a1-2 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
　前記Ａｒａ１－１におけるナフチレン基としては、２，６－ナフチレン基が好ましい。　前記Ａｒａ１－２におけるフェニレン基としては、１，４－フェニレン基が好ましい。 The naphthylene group in Ar a1-1 is preferably a 2,6-naphthylene group. The phenylene group in Ar a1-2 is preferably a 1,4-phenylene group.
　Ａｒａ１－１及びＡｒａ１－２におけるハロゲン原子、アルキル基又はアリール基としては、上記Ａｒａ１において例示したものが挙げられる。 Examples of the halogen atom, alkyl group, or aryl group in Ar a1-1 and Ar a1-2 include those exemplified for Ar a1 above.
　上記で挙げた液晶ポリエステル（Ａ）としては、前記式（Ａ１）で表される繰返し単位のみからなり、前記式（Ａ１）で表される繰返し単位が、下記式（Ａ１－３）で表される繰返し単位、及び下記式（Ａ１－４）で表される繰返し単位を含むことが好ましく、下記式（Ａ１－３）で表される繰返し単位、及び下記式（Ａ１－４）で表される繰返し単位のみからなることがより好ましい。
　（Ａ１－３）－Ｏ－Ａｒａ１－３－ＣＯ－
　（Ａ１－４）－Ｏ－Ａｒａ１－４－ＣＯ－
（Ａｒａ１－３は、２，６－ナフチレン基を表し、
　Ａｒａ１－４は、１，４－フェニレン基を表す。
　Ａｒａ１－３又はＡｒａ１－４で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、炭素数１～１０のアルキル基又は炭素数６～２０のアリール基で置換されていてもよい。） The liquid crystal polyester (A) mentioned above consists only of repeating units represented by the above formula (A1), and the repeating units represented by the above formula (A1) are represented by the following formula (A1-3). It is preferable to include a repeating unit represented by the following formula (A1-4), and a repeating unit represented by the following formula (A1-3), and a repeating unit represented by the following formula (A1-4). More preferably, it consists only of repeating units.
(A1-3)-O-Ar a1-3 -CO-
(A1-4)-O-Ar a1-4 -CO-
(Ar a1-3 represents a 2,6-naphthylene group,
Ar a1-4 represents a 1,4-phenylene group.
The hydrogen atoms in the group represented by Ar a1-3 or Ar a1-4 are each independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Good too. )
　前記式（Ａ１）で表される繰返し単位が、前記式（Ａ１－１）で表される繰返し単位、及び下記式（Ａ１－２）で表される繰返し単位を含む場合、前記液晶ポリエステル（Ａ）を構成する全繰返し単位の合計数（１００％）に対して、一例として、
　前記式（Ａ１－１）で表される繰返し単位の数が４０％超９０％以下で、
　前記式（Ａ１－２）で表される繰返し単位の数は、１０％以上６０％未満であってよく、
　前記式（Ａ１－１）で表される繰返し単位の数が６５％以上８０％以下で、
　前記式（Ａ１－２）で表される繰返し単位の数は、２０％以上３５％以下であってよく、
　前記式（Ａ１－１）で表される繰返し単位の数が７０％以上７５％以下で、
　前記式（Ａ１－２）で表される繰返し単位の数は、２５％以上３０％以下であってよい。
　前記式（Ａ１）で表される繰返し単位が、前記式（Ａ１－３）で表される繰返し単位、及び下記式（Ａ１－４）で表される繰返し単位を含む場合、前記液晶ポリエステル（Ａ）を構成する全繰返し単位の合計数（１００％）に対して、一例として、
　前記式（Ａ１－３）で表される繰返し単位の数が４０％超９０％以下で、
　前記式（Ａ１－４）で表される繰返し単位の数は、１０％以上６０％未満であってよく、
　前記式（Ａ１－３）で表される繰返し単位の数が６５％以上８０％以下で、
　前記式（Ａ１－４）で表される繰返し単位の数は、２０％以上３５％以下であってよく、
　前記式（Ａ１－３）で表される繰返し単位の数が７０％以上７５％以下で、
　前記式（Ａ１－４）で表される繰返し単位の数は、２５％以上３０％以下であってよい。 When the repeating unit represented by the formula (A1) includes a repeating unit represented by the formula (A1-1) and a repeating unit represented by the following formula (A1-2), the liquid crystal polyester (A ), for example, for the total number (100%) of all repeating units constituting
The number of repeating units represented by the formula (A1-1) is more than 40% and not more than 90%,
The number of repeating units represented by the formula (A1-2) may be 10% or more and less than 60%,
The number of repeating units represented by the formula (A1-1) is 65% or more and 80% or less,
The number of repeating units represented by the formula (A1-2) may be 20% or more and 35% or less,
The number of repeating units represented by the formula (A1-1) is 70% or more and 75% or less,
The number of repeating units represented by the formula (A1-2) may be 25% or more and 30% or less.
When the repeating unit represented by the formula (A1) includes a repeating unit represented by the formula (A1-3) and a repeating unit represented by the following formula (A1-4), the liquid crystal polyester (A ), for example, for the total number (100%) of all repeating units constituting
The number of repeating units represented by the formula (A1-3) is more than 40% and less than 90%,
The number of repeating units represented by the formula (A1-4) may be 10% or more and less than 60%,
The number of repeating units represented by the formula (A1-3) is 65% or more and 80% or less,
The number of repeating units represented by the formula (A1-4) may be 20% or more and 35% or less,
The number of repeating units represented by the formula (A1-3) is 70% or more and 75% or less,
The number of repeating units represented by the formula (A1-4) may be 25% or more and 30% or less.
　液晶ポリエステル（Ａ）は、前記式（Ａ１）で表される繰返し単位を、それぞれ独立に、２種以上有してよい。また、液晶ポリエステルは、前記式（Ａ１）で表される繰返し単位以外の繰返し単位を有してもよいが、その含有量は、液晶ポリエステル（Ａ）を構成する全繰返し単位の合計数（１００％）に対して、１０％以下が好ましく、５％以下がより好ましい。 The liquid crystal polyester (A) may each independently have two or more types of repeating units represented by the formula (A1). In addition, the liquid crystal polyester may have repeating units other than the repeating unit represented by the formula (A1), but the content thereof is determined by the total number of all repeating units constituting the liquid crystal polyester (A) (100 %), preferably 10% or less, more preferably 5% or less.
　本明細書において、各繰返し単位の数は、特開２０００－１９１６８号公報に記載の分析方法によって求められる値を意味する。
　具体的には、液晶ポリエステル樹脂を超臨界状態の炭素数１～３のアルコールと反応させて、前記液晶ポリエステル樹脂をその繰返し単位を誘導するモノマーまで解重合し、解重合生成物として得られる各繰返し単位を誘導するモノマーを液体クロマトグラフィーによって定量することで、各繰返し単位の数を算出することができる。 In this specification, the number of each repeating unit means a value determined by the analysis method described in JP-A-2000-19168.
Specifically, a liquid crystal polyester resin is reacted with an alcohol having 1 to 3 carbon atoms in a supercritical state to depolymerize the liquid crystal polyester resin to a monomer that induces its repeating unit, and each of the depolymerized products obtained is The number of each repeating unit can be calculated by quantifying the monomer that induces the repeating unit by liquid chromatography.
　液晶ポリエステルの流動開始温度は、２６０℃以上が好ましく、２６０℃以上４００℃以下がより好ましく、２６０℃以上３８０℃以下がより好ましく、２６０℃以上３２０℃以下がより好ましく、２８０℃以上３１０℃以下がさらに好ましい。 The flow start temperature of the liquid crystal polyester is preferably 260°C or higher, more preferably 260°C or higher and 400°C or lower, more preferably 260°C or higher and 380°C or lower, more preferably 260°C or higher and 320°C or lower, and 280°C or higher and 310°C or lower. is even more preferable.
　流動開始温度は、フローテスターを用いて、液晶ポリエステルを９．８ＭＰａ（１００ｋｇ／ｃｍ２）の荷重下４℃／分の速度で昇温しながら溶融させ、内径１ｍｍ及び長さ１０ｍｍのノズルから押し出すときに、液晶ポリエステルが４８００Ｐａ・ｓ（４８０００ポイズ）の粘度を示すときの温度を意味する。 The flow start temperature is determined by melting the liquid crystal polyester using a flow tester while increasing the temperature at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm 2 ), and extruding it from a nozzle with an inner diameter of 1 mm and a length of 10 mm. Sometimes, it means the temperature at which the liquid crystal polyester exhibits a viscosity of 4800 Pa·s (48000 poise).
（液晶ポリエステルの製造方法）
　液晶ポリエステルは、それを構成する繰返し単位に対応する原料モノマーを溶融重合させ、必要に応じて得られた重合物を固相重合させることにより、製造することが好ましい。
　溶融重合は、触媒の存在下に行ってもよい。 (Method for manufacturing liquid crystal polyester)
The liquid crystal polyester is preferably produced by melt polymerizing raw material monomers corresponding to the repeating units constituting the polyester and, if necessary, solid-phase polymerizing the obtained polymer.
Melt polymerization may be carried out in the presence of a catalyst.
（液晶ポリエステルを含む組成物）
　本実施形態における液晶ポリエステルを含む組成物は、組成物の総質量１００質量％に対して、液晶ポリエステルを８０質量％以上含むことが好ましく、９０質量％以上含むことがより好ましく、１００質量％含むことがさらに好ましい。
　前記組成物は、上述した液晶ポリエステル以外の任意成分を更に含有していてもよい。 (Composition containing liquid crystal polyester)
The composition containing liquid crystal polyester in this embodiment preferably contains 80 mass % or more, more preferably 90 mass % or more, and 100 mass % of liquid crystal polyester based on 100 mass % of the total mass of the composition. It is even more preferable.
The composition may further contain optional components other than the above-mentioned liquid crystal polyester.
　任意成分としては、充填剤、液晶ポリエステル以外の樹脂、難燃剤、導電性付与材剤、結晶核剤、紫外線吸収剤、酸化防止剤、制振剤、抗菌剤、防虫剤、防臭剤、着色防止剤、熱安定剤、離型剤、帯電防止剤、可塑剤、滑剤、染料、発泡剤、制泡剤、粘度調整剤、界面活性剤等が挙げられる。 Optional ingredients include fillers, resins other than liquid crystal polyester, flame retardants, conductivity imparting materials, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and color prevention agents. agent, heat stabilizer, mold release agent, antistatic agent, plasticizer, lubricant, dye, foaming agent, antifoaming agent, viscosity modifier, surfactant, etc.
　前記組成物の形状は、例えば粉末状やペレット状であってよい。 The shape of the composition may be, for example, powder or pellet.
　前記組成物の流動開始温度の好ましい値としては、前記液晶ポリエステルの流動開始温度として例示した各数値が挙げられる。 Preferred values for the flow start temperature of the composition include the values exemplified as the flow start temperature of the liquid crystal polyester.
　ＦＴの温度（℃）と、Ｔｒの温度（℃）の差（ＦＴ－Ｔｒ）の値が大きいほど、表面平滑性により優れたフィルムを容易に製造可能である。
　ＦＴ－Ｔｒ（℃）の値は、１５℃以上３０℃以下であってよく、１８℃以上２６℃以下であってよい。 The larger the value of the difference (FT-Tr) between the FT temperature (°C) and the Tr temperature (°C), the easier it is to produce a film with more excellent surface smoothness.
The value of FT-Tr (°C) may be 15°C or more and 30°C or less, and may be 18°C or more and 26°C or less.
　本実施形態のフィルムの製造方法によれば、製造されるフィルム表面の表面平滑性を向上させる観点からは、ダイの温度を高く設定しないことが有効である。これは、ダイの設定温度がＦＴ又はＴｒに比べて高い場合は、ダイから吐出したときの液晶ポリエステルの粘度が低下して、製造過程でのフィルムの張力が不十分となり、フィルムの表面平滑性を低下させる要因となるからであると考えられる。 According to the film manufacturing method of the present embodiment, it is effective not to set the die temperature high from the viewpoint of improving the surface smoothness of the surface of the manufactured film. This is because if the set temperature of the die is higher than FT or Tr, the viscosity of the liquid crystal polyester when discharged from the die decreases, and the tension of the film during the manufacturing process is insufficient, resulting in poor surface smoothness of the film. This is thought to be because it becomes a factor that reduces the
＜液晶ポリエステルフィルム＞
　実施形態のフィルムは、下記式（Ａ１）で表される繰返し単位を含む液晶ポリエステル（Ａ）を含有し、
　（Ａ１）－Ｏ－Ａｒａ１－ＣＯ－
（Ａｒａ１は、フェニレン基、ナフチレン基又はビフェニリレン基を表し、
　Ａｒａ１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）
　表面粗さ（Ｒａ）の値が１．０μｍ以下である。 <Liquid crystal polyester film>
The film of the embodiment contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1),
(A1)-O-Ar a1 -CO-
(Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
The hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
The value of surface roughness (Ra) is 1.0 μm or less.
　実施形態のフィルムは、液晶ポリエステル（Ａ）を含有する組成物から製造可能であるため、表面粗さＲａで規定される表面平滑性に優れる。 Since the film of the embodiment can be manufactured from a composition containing liquid crystal polyester (A), it has excellent surface smoothness defined by surface roughness Ra.
　実施形態のフィルムの表面粗さ（Ｒａ）の値は、１．０μｍ以下であり、０．７μｍ以下であってよく、０．２μｍ以上０．７μｍ以下であってよい。表面粗さ（Ｒａ）の値は、０．２μｍ以上０．６μｍ以下であってよく、０．２μｍ以上０．５μｍ以下であってよく、０．３μｍ以上０．７μｍ以下であってよく、０．３μｍ以上０．６μｍ以下であってよく、０．３μｍ以上０．５μｍ以下であってよい。
　実施形態のフィルムにおいて、少なくともフィルムの片面の表面粗さ（Ｒａ）の値が、１．０μｍ以下であり、０．７μｍ以下であってよく、０．２μｍ以上０．６μｍ以下であってよく、０．２μｍ以上０．５μｍ以下であってよく、０．３μｍ以上０．７μｍ以下であってよく、０．３μｍ以上０．６μｍ以下であってよく、０．３μｍ以上０．５μｍ以下であってよい。
　実施形態のフィルムにおいて、両面のフィルムの表面粗さ（Ｒａ）の値が、１．０μｍ以下であってよく、０．７μｍ以下であってよく、０．２μｍ以上０．７μｍ以下であってよく、０．２μｍ以上０．６μｍ以下であってよく、０．２μｍ以上０．５μｍ以下であってよく、０．３μｍ以上０．７μｍ以下であってよく、０．３μｍ以上０．６μｍ以下であってよく、０．３μｍ以上０．５μｍ以下であってよい。 The value of the surface roughness (Ra) of the film of the embodiment is 1.0 μm or less, may be 0.7 μm or less, and may be 0.2 μm or more and 0.7 μm or less. The value of surface roughness (Ra) may be 0.2 μm or more and 0.6 μm or less, 0.2 μm or more and 0.5 μm or less, 0.3 μm or more and 0.7 μm or less, and 0. It may be .3 μm or more and 0.6 μm or less, and may be 0.3 μm or more and 0.5 μm or less.
In the film of the embodiment, the surface roughness (Ra) value of at least one side of the film is 1.0 μm or less, may be 0.7 μm or less, and may be 0.2 μm or more and 0.6 μm or less, It may be 0.2 μm or more and 0.5 μm or less, 0.3 μm or more and 0.7 μm or less, 0.3 μm or more and 0.6 μm or less, and 0.3 μm or more and 0.5 μm or less. good.
In the film of the embodiment, the surface roughness (Ra) value of the film on both sides may be 1.0 μm or less, 0.7 μm or less, or 0.2 μm or more and 0.7 μm or less. , may be 0.2 μm or more and 0.6 μm or less, 0.2 μm or more and 0.5 μm or less, 0.3 μm or more and 0.7 μm or less, and 0.3 μm or more and 0.6 μm or less. It may be 0.3 μm or more and 0.5 μm or less.
　液晶ポリエステルフィルムにおける、液晶ポリエステルとしては、上記の実施形態のフィルムの製造方法で例示したものが挙げられる。 Examples of the liquid crystal polyester in the liquid crystal polyester film include those exemplified in the film manufacturing method of the above embodiment.
　実施形態のフィルムが含有する前記液晶ポリエステルは、液晶ポリエステル（Ａ）のみからなるものであってもよい。 The liquid crystal polyester contained in the film of the embodiment may consist only of liquid crystal polyester (A).
　前記液晶ポリエステル（Ａ）を構成する全繰返し単位の合計数（１００％）に対して、前記式（Ａ１）で表される繰返し単位の数は、４０％以上、４０％超、５０％以上、５０％超、６０％以上、６０％超、７０％以上、７０％超、８０％以上、８０％超、８５％以上、８５％超、９０％以上、９０％超、９５％以上、９５％超、９８％以上、又は９８％超であってよく、前記式（Ａ１）で表される繰返し単位のみからなってよい（すなわち、前記式（Ａ１）で表される繰返し単位の数が１００％であってよい）。 Relative to the total number (100%) of all repeating units constituting the liquid crystal polyester (A), the number of repeating units represented by the formula (A1) is 40% or more, more than 40%, 50% or more, Over 50%, over 60%, over 60%, over 70%, over 70%, over 80%, over 80%, over 85%, over 85%, over 90%, over 90%, over 95%, 95% may be more than 98%, or more than 98%, and may consist only of repeating units represented by formula (A1) (i.e., the number of repeating units represented by formula (A1) is 100%). ).
　液晶ポリエステルフィルムにおける、液晶ポリエステル（Ａ）としては、前記式（Ａ１）で表される繰返し単位のみからなり、前記式（Ａ１）で表される繰返し単位が、前記式（Ａ１－３）で表される繰返し単位、及び前記式（Ａ１－４）で表される繰返し単位を含むことが好ましく、前記式（Ａ１－３）で表される繰返し単位、及び前記式（Ａ１－４）で表される繰返し単位のみからなることがより好ましい。 In the liquid crystal polyester film, the liquid crystal polyester (A) consists only of repeating units represented by the above formula (A1), and the repeating units represented by the above formula (A1) are represented by the above formula (A1-3). It is preferable to include a repeating unit represented by the above formula (A1-4), and a repeating unit represented by the above formula (A1-3), and a repeating unit represented by the above formula (A1-4). More preferably, it consists of only repeating units.
　フィルムは、液晶ポリエステル以外の任意成分を更に含有していてもよい。任意成分としては、上記の実施形態のフィルムの製造方法で例示したものが挙げられる。 The film may further contain optional components other than the liquid crystal polyester. Examples of optional components include those exemplified in the film manufacturing method of the above embodiment.
　液晶ポリエステルに含有される液晶ポリエステル、及び所望により含有されてもよい任意成分の種類や含有量としては、上記の実施形態のフィルムの製造方法の組成物において例示したものと同一のものが挙げられる。 The types and contents of the liquid crystal polyester contained in the liquid crystal polyester and optional components that may be contained as desired include those same as those exemplified in the composition of the film manufacturing method of the above embodiment. .
　実施形態のフィルムの厚さは、３０μｍ以上３００μｍ以下であってよく、３０μｍ以上２００μｍ以下であってよく、５０μｍ以上２００μｍ以下であってよい。
　フィルムの厚さは、フィルムの外周から５ｍｍ以上内側の部分に対し、９箇所以上計測した値の平均値とする。 The thickness of the film of the embodiment may be 30 μm or more and 300 μm or less, 30 μm or more and 200 μm or less, and 50 μm or more and 200 μm or less.
The thickness of the film is the average value of the values measured at 9 or more points on a portion 5 mm or more inside the outer periphery of the film.
　実施形態のフィルムは、上記の実施形態のフィルムの製造方法により製造されたものであってよい。 The film of the embodiment may be manufactured by the method of manufacturing the film of the embodiment described above.
　実施形態のフィルムによれば、表面平滑性に優れたフィルムを提供できる。 According to the film of the embodiment, a film with excellent surface smoothness can be provided.
　次に実施例を示して本開示をさらに詳細に説明するが、本開示は以下の実施例に限定されるものではない。 Next, the present disclosure will be described in further detail by showing examples, but the present disclosure is not limited to the following examples.
≪測定・評価≫
〔液晶ポリエステルの流動開始温度（ＦＴ）の測定〕
　フローテスターＣＦＴ－５００ＥＸ（株式会社島津製作所製）を用いて、液晶ポリエステル約２ｇを、内径１ｍｍ及び長さ１０ｍｍのノズルを有するダイを取り付けたシリンダーに充填し、９．８ＭＰａ（１００ｋｇ／ｃｍ２）の荷重下、４℃／分の速度で昇温しながら、液晶ポリエステルを溶融させ、ノズルから押し出した。当該液晶ポリエステルが４８００Ｐａ・ｓ（４８０００Ｐ）の粘度を示す温度を測定し、当該温度を液晶ポリエステルの流動開始温度とした。 ≪Measurement/Evaluation≫
[Measurement of flow start temperature (FT) of liquid crystal polyester]
Using a flow tester CFT-500EX (manufactured by Shimadzu Corporation), about 2 g of liquid crystal polyester was filled into a cylinder equipped with a die having a nozzle with an inner diameter of 1 mm and a length of 10 mm, and the pressure was 9.8 MPa (100 kg/cm 2 ). The liquid crystal polyester was melted and extruded from the nozzle while increasing the temperature at a rate of 4°C/min under a load of . The temperature at which the liquid crystal polyester exhibits a viscosity of 4800 Pa·s (48000 P) was measured, and this temperature was defined as the flow start temperature of the liquid crystal polyester.
〔液晶ポリエステルのＴｒの測定〕
　以下の条件で、回転式レオメータＤｉｓｃｏｖｅｒｙ　ＨＲ－２０（ＴＡインスツルメント株式会社製）を用いて、液晶ポリエステルを３６０℃で溶融させた後に降温速度５℃／ｍｉｎで冷却し、液晶ポリエステルの粘度を測定した。液晶ポリエステルの粘度が１．０×１０４Ｐａ・ｓになる温度をＴｒとした。
　測定開始温度：３６０℃
　降温速度　　：５℃／ｍｉｎ
　ひずみ　　　：０．０５％
　周波数　　　：１Ｈｚ
　使用プレート：２５ｍｍφパラレルプレート [Measurement of Tr of liquid crystal polyester]
Under the following conditions, using a rotary rheometer Discovery HR-20 (manufactured by TA Instruments Co., Ltd.), liquid crystal polyester was melted at 360°C and then cooled at a cooling rate of 5°C/min to determine the viscosity of the liquid crystal polyester. It was measured. The temperature at which the viscosity of the liquid crystal polyester became 1.0×10 4 Pa·s was defined as Tr.
Measurement start temperature: 360℃
Cooling rate: 5℃/min
Strain: 0.05%
Frequency: 1Hz
Plate used: 25mmφ parallel plate
〔フィルム厚さ〕
　フィルムを長さ方向に１５０ｍｍの長さで切り出した。フィルムの幅方向の両端から５ｍｍの位置及び中心の位置に計３本の線（直線）を引いた。
　長さ方向も同様に、両端から５ｍｍの位置及び中心の位置に計３本の線（直線）を引いた。　これら計６本の線が交差する９点について、Ｕ字形鋼板マイクロメータ（ＰＭＵ１５０－２５ＭＪ（株式会社ミツトヨ製））を用いて、各箇所の厚さを測定し、算術平均値を算出し、フィルム厚さとした。 [Film thickness]
The film was cut into a length of 150 mm in the longitudinal direction. A total of three lines (straight lines) were drawn at positions 5 mm from both ends of the film in the width direction and at the center.
Similarly, a total of three lines (straight lines) were drawn in the length direction at positions 5 mm from both ends and at the center. Using a U-shaped steel plate micrometer (PMU150-25MJ (manufactured by Mitutoyo Co., Ltd.)), the thickness of each location was measured at the nine points where these six lines intersect, and the arithmetic mean value was calculated. It was thick.
〔フィルムの表面粗さの測定〕
　以下の条件で、表面粗さ計（ＳＥ６００ＬＫ３１（株式会社小坂研究所製））を用いてフィルム幅方向の算術平均粗さ（Ｒａ）を測定した。フィルムの片面に対して算術平均粗さ（Ｒａ）の測定を行った。
　触針先端半径：２μｍ
　触針速度　　：０．５ｍｍ／ｓｅｃ
　測定力　　　：０．７５ｍＮ
　測定長　　　：４ｍｍ
　カットオフ値：０．８ｍｍ [Measurement of film surface roughness]
The arithmetic mean roughness (Ra) in the width direction of the film was measured using a surface roughness meter (SE600LK31 (manufactured by Kosaka Laboratory Co., Ltd.)) under the following conditions. Arithmetic mean roughness (Ra) was measured on one side of the film.
Stylus tip radius: 2μm
Stylus speed: 0.5mm/sec
Measuring force: 0.75mN
Measurement length: 4mm
Cutoff value: 0.8mm
≪製造≫
［製造例１］
・液晶ポリエステルの製造
　撹拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、２－ヒドロキシ－６－ナフトエ酸　１５１１．１ｇ（８．０３モル）、ｐ－ヒドロキシ安息香酸　４１０．２ｇ（２．９７モル）、無水酢酸　１２９１．４ｇ（１２．６５モル）及び１－メチルイミダゾール　０．０５８ｇを添加した。内容物を窒素ガス気流下で撹拌しながら、１時間かけて内温が室温から１４０℃になるまで昇温し、１４０℃で１時間撹拌した。
　次いで、留出する副生酢酸及び未反応の無水酢酸を留去しながら、内容物を１４０℃から２７５℃まで２時間５０分かけて昇温した。内容物を２７５℃で３時間保持した後、反応器から取り出した。取り出した内容物を室温に冷却し、粉砕機で粉砕して粉末状の液晶ポリエステル（ａ）を得た。この液晶ポリエステル（ａ）を、窒素雰囲気下で室温から１９０℃まで１時間１０分かけて昇温した後、１９０℃から２６０℃まで１１時間４０分かけて昇温した。次いで２６０℃で１０時間保温し、固相重合を行った。得られた固相重合物を室温まで冷却して、粉末状の液晶ポリエステル（ｂ）を得た。
　次いで、２軸押出機（池貝鉄工株式会社製、ＰＣＭ－３０）を用いて、液晶ポリエステル（ｂ）をシリンダー温度３２０℃で造粒し、ペレット状の液晶ポリエステル（ｃ）を得た。液晶ポリエステル（ｃ）の流動開始温度（ＦＴ）は２９０℃であった。液晶ポリエステル（ｃ）のＴｒは２６８℃であった。 ≪Manufacturing≫
[Manufacture example 1]
・Production of liquid crystal polyester 1511.1 g (8.03 mol) of 2-hydroxy-6-naphthoic acid and p-hydroxy were placed in a reactor equipped with a stirring device, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser. 410.2 g (2.97 moles) of benzoic acid, 1291.4 g (12.65 moles) of acetic anhydride, and 0.058 g of 1-methylimidazole were added. While stirring the contents under a nitrogen gas stream, the internal temperature was raised from room temperature to 140°C over 1 hour, and the mixture was stirred at 140°C for 1 hour.
Next, the temperature of the contents was raised from 140° C. to 275° C. over 2 hours and 50 minutes while distilling off by-product acetic acid and unreacted acetic anhydride. The contents were held at 275° C. for 3 hours before being removed from the reactor. The contents taken out were cooled to room temperature and pulverized with a pulverizer to obtain powdered liquid crystal polyester (a). The temperature of this liquid crystal polyester (a) was raised from room temperature to 190°C over 1 hour and 10 minutes under a nitrogen atmosphere, and then from 190°C to 260°C over 11 hours and 40 minutes. Next, the mixture was kept at 260° C. for 10 hours to carry out solid phase polymerization. The obtained solid phase polymer was cooled to room temperature to obtain a powdery liquid crystal polyester (b).
Next, the liquid crystal polyester (b) was granulated using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM-30) at a cylinder temperature of 320° C. to obtain a pellet-shaped liquid crystal polyester (c). The flow start temperature (FT) of the liquid crystal polyester (c) was 290°C. The liquid crystal polyester (c) had a Tr of 268°C.
［実施例１］
　上記で製造したペレット状の液晶ポリエステル（ｃ）を成形材料として用い、インフレーション法によりフィルムを製造した。
　液晶ポリエステル（ｃ）のペレット（組成物）をシリンダー内径２０ｍｍの単軸押出機のシリンダー内へ投入し、シリンダー温度２９５℃、スクリュー回転数３０ｒｐｍの条件で混練し、ダイ内径２０ｍｍ、ダイギャップ１．１５ｍｍの環状ダイから組成物を押出すインフレーション法を行い、フィルム折幅８０ｍｍにて、実施例１のフィルムを製造した。 [Example 1]
A film was manufactured by an inflation method using the pelletized liquid crystal polyester (c) manufactured above as a molding material.
Pellets (composition) of liquid crystal polyester (c) were put into the cylinder of a single-screw extruder with a cylinder inner diameter of 20 mm, and kneaded under the conditions of a cylinder temperature of 295° C. and a screw rotation speed of 30 rpm, and a die inner diameter of 20 mm and a die gap of 1. The film of Example 1 was manufactured using an inflation method in which the composition was extruded from a 15 mm annular die with a film fold width of 80 mm.
　上記ダイは３つの部分から構成されており、部分ごとに独立に温度設定が可能であった。上記の組成物を吐出する吐出口を有する環状ダイ部分を含め、３分割された各ダイの部分の設定温度は、いずれも２７５℃とした。 The die described above was composed of three parts, and the temperature could be set independently for each part. The set temperature of each of the three divided die parts, including the annular die part having a discharge port for discharging the above composition, was 275°C.
［実施例２～６］
　実施例１において、装置のダイの設定温度、シリンダー温度、スクリュー回転数、及びフィルム折幅を、表１に示すとおり変更した以外は、上記実施例１と同様にして、各実施例２～６のフィルムを製造した。３分割されたダイの設定温度は、互いに同一の温度とした。 [Examples 2 to 6]
In Example 1, each of Examples 2 to 6 was carried out in the same manner as in Example 1, except that the set temperature of the die of the apparatus, the cylinder temperature, the screw rotation speed, and the film folding width were changed as shown in Table 1. A film was produced. The set temperatures of the three divided dies were set to be the same temperature.
　液晶ポリエステル及びフィルムについて、上記の各項目を測定した結果を表１に示す。 Table 1 shows the results of measuring each of the above items for the liquid crystal polyester and film.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～６の結果から、－１０≦ＦＴ－ダイの設定温度（℃）≦３０の条件を満たし製造された実施例１～６のフィルムは、フィルムの表面粗さＲａの値が小さく、表面平滑性に優れていた。 From the results of Examples 1 to 6, the films of Examples 1 to 6 that were manufactured satisfying the condition of -10≦FT-die setting temperature (°C)≦30 had small values of surface roughness Ra of the film, It had excellent surface smoothness.
　本開示によれば、液晶ポリエステルを含有し、表面平滑性に優れたフィルムを製造可能である。 According to the present disclosure, it is possible to produce a film containing liquid crystal polyester and having excellent surface smoothness.
　１…フィルム
　２…チューブフィルム
　１０…製造装置
　１１…押出機
　１２…ダイ
　１４…ガイド板
　１６…ニップロール
　１１１…シリンダー
　１１２…スクリュー
　１２１…ダイ下部
　１２２…ダイ中部
　１２３…ダイ上部
　Ｍ…流動物 1... Film 2... Tube film 10... Manufacturing equipment 11... Extruder 12... Die 14... Guide plate 16... Nip roll 111... Cylinder 112... Screw 121... Die lower part 122... Die middle part 123... Die upper part M... Fluid object

Claims (9)

  1. 　液晶ポリエステルを含む組成物を、以下の条件でダイから押し出して、フィルムを成形することを含む、フィルムの製造方法。
    　－１０≦ＦＴ－前記ダイの設定温度（℃）≦３０
    　ＦＴ：前記液晶ポリエステルの流動開始温度（℃）     A method for producing a film, which comprises extruding a composition containing liquid crystal polyester through a die under the following conditions to form a film.
    -10≦FT-Set temperature of the die (℃)≦30
    FT: Flow start temperature of the liquid crystal polyester (°C)
  2. 　前記ダイの設定温度がさらに以下の条件を満たす、請求項１に記載のフィルムの製造方法。
    　－３５≦Ｔｒ－前記ダイの設定温度（℃）≦１０
    　Ｔｒ：前記組成物の下記測定条件で測定された粘度が１．０×１０４Ｐａ・ｓとなる温度（℃）
    　測定条件：
    　装置：回転式レオメータ
    　降温速度：５℃／ｍｉｎ
    　ひずみ：０．０５％
    　周波数：１Ｈｚ     The method for producing a film according to claim 1, wherein the temperature setting of the die further satisfies the following conditions.
    -35≦Tr-Set temperature of the die (°C)≦10
    Tr: Temperature (°C) at which the viscosity of the composition measured under the following measurement conditions is 1.0 × 10 4 Pa・s
    Measurement condition:
    Equipment: Rotary rheometer Cooling rate: 5℃/min
    Strain: 0.05%
    Frequency: 1Hz
  3. 　前記液晶ポリエステルは、
    　下記式（Ａ１）で表される繰返し単位を含む液晶ポリエステル（Ａ）を含有する、請求項１又は２に記載のフィルムの製造方法。
    　（Ａ１）－Ｏ－Ａｒａ１－ＣＯ－
    （Ａｒａ１は、フェニレン基、ナフチレン基又はビフェニリレン基を表し、
    　Ａｒａ１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）     The liquid crystal polyester is
    The method for producing a film according to claim 1 or 2, comprising a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1).
    (A1)-O-Ar a1 -CO-
    (Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
    The hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
  4. 　前記液晶ポリエステル（Ａ）を構成する全繰返し単位の合計数（１００％）に対して、前記式（Ａ１）で表される繰返し単位の数が４０％超である、請求項３に記載のフィルムの製造方法。 The film according to claim 3, wherein the number of repeating units represented by the formula (A1) is more than 40% with respect to the total number (100%) of all repeating units constituting the liquid crystal polyester (A). manufacturing method.
  5. 　前記液晶ポリエステル（Ａ）が、前記式（Ａ１）で表される繰返し単位のみからなる、請求項３に記載のフィルムの製造方法。 The method for producing a film according to claim 3, wherein the liquid crystal polyester (A) consists only of repeating units represented by the formula (A1).
  6. 　前記液晶ポリエステル（Ａ）は、
    　下記式（Ａ１－１）で表される繰返し単位を含む、請求項３に記載のフィルムの製造方法。
    　（Ａ１－１）－Ｏ－Ａｒａ１－１－ＣＯ－
    （Ａｒａ１－１は、ナフチレン基を表し、
    　Ａｒａ１－１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）     The liquid crystal polyester (A) is
    The method for producing a film according to claim 3, comprising a repeating unit represented by the following formula (A1-1).
    (A1-1)-O-Ar a1-1 -CO-
    (Ar a1-1 represents a naphthylene group,
    The hydrogen atoms in the group represented by Ar a1-1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
  7. 　前記式（Ａ１）に該当する繰返し単位の合計数（１００％）に対し、前記式（Ａ１－１）で表される繰返し単位の数が４０％超９０％以下である、請求項６に記載のフィルムの製造方法。 According to claim 6, the number of repeating units represented by the formula (A1-1) is more than 40% and 90% or less with respect to the total number (100%) of repeating units corresponding to the formula (A1). A method for producing a film.
  8. 　前記成形が、インフレーション法又はＴダイ法による成形である、請求項１又は２に記載のフィルムの製造方法。 The method for producing a film according to claim 1 or 2, wherein the molding is performed by an inflation method or a T-die method.
  9. 　下記式（Ａ１）で表される繰返し単位を含む液晶ポリエステル（Ａ）を含有し、
    　（Ａ１）－Ｏ－Ａｒａ１－ＣＯ－
    （Ａｒａ１は、フェニレン基、ナフチレン基又はビフェニリレン基を表し、
    　Ａｒａ１で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）
    　表面粗さ（Ｒａ）の値が１．０μｍ以下である、フィルム。     Contains a liquid crystal polyester (A) containing a repeating unit represented by the following formula (A1),
    (A1)-O-Ar a1 -CO-
    (Ar a1 represents a phenylene group, a naphthylene group or a biphenylylene group,
    The hydrogen atoms in the group represented by Ar a1 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group. )
    A film having a surface roughness (Ra) of 1.0 μm or less.
PCT/JP2023/020794 2022-06-07 2023-06-05 Method for producing film WO2023238819A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011096471A (en) * 2009-10-29 2011-05-12 Sumitomo Chemical Co Ltd Cable for mobile phone with shield layer
WO2018235436A1 (en) * 2017-06-22 2018-12-27 デンカ株式会社 Laminate comprising thermoplastic engineering plastic layer and method for producing same
JP2019081377A (en) * 2019-02-12 2019-05-30 東洋紡株式会社 Thermoplastic resin sheet and molded article obtained by heat-molding the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011096471A (en) * 2009-10-29 2011-05-12 Sumitomo Chemical Co Ltd Cable for mobile phone with shield layer
WO2018235436A1 (en) * 2017-06-22 2018-12-27 デンカ株式会社 Laminate comprising thermoplastic engineering plastic layer and method for producing same
JP2019081377A (en) * 2019-02-12 2019-05-30 東洋紡株式会社 Thermoplastic resin sheet and molded article obtained by heat-molding the same

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