WO2012105468A1 - Feuille stratifiée et son utilisation - Google Patents

Feuille stratifiée et son utilisation Download PDF

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Publication number
WO2012105468A1
WO2012105468A1 PCT/JP2012/051920 JP2012051920W WO2012105468A1 WO 2012105468 A1 WO2012105468 A1 WO 2012105468A1 JP 2012051920 W JP2012051920 W JP 2012051920W WO 2012105468 A1 WO2012105468 A1 WO 2012105468A1
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Prior art keywords
liquid crystal
crystal polyester
group
layer
repeating unit
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PCT/JP2012/051920
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English (en)
Japanese (ja)
Inventor
細田　朋也
光男 前田
岡本　敏
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住友化学株式会社
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Publication of WO2012105468A1 publication Critical patent/WO2012105468A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/145—Carbon only, e.g. carbon black, graphite
    • 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
    • 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
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • 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
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier

Definitions

  • the present invention relates to a laminated sheet having a graphite layer and a liquid crystal polyester layer.
  • Graphite is a conductor having an appropriate resistance, and is therefore used as a material for a planar heating element.
  • graphite is used as a material for a heat dissipation sheet because of its excellent thermal conductivity.
  • the graphite layer and protective layer are used to prevent the graphite from deteriorating due to oxygen and water vapor in the air and the resistance and thermal conductivity of the graphite from changing.
  • it is used in the form of a laminated sheet having a resin layer, and as a material for this resin layer, liquid crystal polyester has been studied because it is excellent in low water absorption or gas barrier properties.
  • Patent Document 1 discloses a predetermined product (Xydar, Vectra) as a liquid crystal polyester used for the material of the resin layer.
  • Patent Document 2 does not describe the use of graphite as a material for the planar heating element, but a functional material that reacts with the liquid crystalline polyester using liquid crystal polyester as a continuous phase as the material for the resin layer of the planar heating element.
  • a liquid crystal polyester composition having a copolymer having a group as a dispersed phase is disclosed.
  • As the liquid crystal polyester 60 mol% of repeating units derived from p-hydroxybenzoic acid and 15 structural units derived from terephthalic acid are disclosed. Specifically disclosed are those having 5 mol% of structural units derived from isophthalic acid, 5 mol% of structural units derived from isophthalic acid, and 20 mol% of structural units derived from 4,4-dihydroxybiphenyl.
  • an object of the present invention is to provide a laminated sheet that has a graphite layer and a liquid crystal polyester layer, has an excellent water vapor barrier property of the liquid crystal polyester layer, and is suitably used as a planar heating element or a heat dissipation sheet.
  • the present invention includes a graphite layer and a liquid crystal polyester layer disposed on at least one surface thereof, wherein the liquid crystal polyester layer is represented by the following formula (1). And a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3), the content of the repeating unit containing 2,6-naphthylene group is Provided is a laminated sheet which is a layer composed of liquid crystal polyester of 40 mol% or more based on the total amount.
  • Ar 1 represents a 2,6-naphthylene group, a 1,4-phenylene group or a 4,4′-biphenylylene group.
  • Ar 2 and Ar 3 are each independently a 2,6-naphthylene group, 1,4 Represents a -phenylene group, a 1,3-phenylene group or a 4,4′-biphenylylene group, wherein the hydrogen atoms in the group represented by Ar 1 , Ar 2 or Ar 3 are each independently a halogen atom or an alkyl group; Alternatively, it may be substituted with an aryl group.
  • the present invention also includes a graphite layer and a liquid crystal polyester layer disposed on at least one surface thereof, and the water vapor permeability measured at a temperature of 40 ° C. and a relative humidity of 90% of the liquid crystal polyester layer.
  • a laminated sheet of 0.005 g / m 2 ⁇ 24 h or less.
  • the present invention includes a graphite layer and a liquid crystal polyester layer disposed on at least one surface thereof, and the liquid crystal polyester layer has a temperature of 40 ° C. and a relative humidity of 90 when the film has a thickness of 50 ⁇ m.
  • a laminated sheet which is a layer composed of a liquid crystal polyester having a water vapor permeability measured in% of 0.005 g / m 2 ⁇ 24 h or less is provided.
  • the present invention provides a planar heating element and a heat dissipation sheet using any one of the above laminated sheets.
  • the laminated sheet of the present invention is excellent in the water vapor barrier property of the liquid crystal polyester layer, and by using this, it is possible to obtain a sheet heating element and a heat radiating sheet having excellent performance sustainability.
  • the laminated sheet of the present invention has a graphite layer and a liquid crystal polyester layer.
  • the liquid crystalline polyester constituting the liquid crystalline polyester layer is a polyester that exhibits optical anisotropy when melted, and is preferably a repeating unit represented by the following formula (1) (hereinafter referred to as a repeating unit (1)).
  • a repeating unit represented by the following formula (2) hereinafter sometimes referred to as repeating unit (2)
  • a repeating unit represented by the following formula (3) hereinafter referred to as repeating unit (3). And so on).
  • Ar 1 represents a 2,6-naphthylene group, a 1,4-phenylene group or a 4,4′-biphenylylene group.
  • Ar 2 and Ar 3 are each independently a 2,6-naphthylene group, 1,4 -Represents a phenylene group, a 1,3-phenylene group or a 4,4′-biphenylylene group, wherein the hydrogen atom in the group represented by Ar 1 , Ar 2 or Ar 3 is independently a halogen atom or a carbon number (It may be substituted with an alkyl group of 1 to 10 or an aryl group of 6 to 20 carbon atoms.)
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, Examples thereof include an n-octyl group and an n-decyl group, and the carbon number thereof is usually 1 to 10.
  • aryl group examples include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group, and the number of carbon atoms is usually 6-20.
  • the hydrogen atom is substituted with these groups, the number is usually 2 or less for each group represented by Ar 1 , Ar 2 or Ar 3 , and preferably 1 It is as follows.
  • the repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid.
  • the repeating unit (1) those in which Ar 1 is a 2,6-naphthylene group, that is, a repeating unit derived from 6-hydroxy-2-naphthoic acid is preferable.
  • the repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid.
  • Ar 2 is a 2,6-naphthylene group, that is, a repeating unit derived from 2,6-naphthalenedicarboxylic acid, and Ar 2 is a 1,4-phenylene group, Repeating units derived from terephthalic acid are preferred.
  • the repeating unit (3) is a repeating unit derived from a predetermined aromatic diol.
  • Ar 3 is a 1,4-phenylene group, that is, a repeating unit derived from hydroquinone, and Ar 3 is a 4,4′-biphenylylene group, that is, 4,4′-. Repeating units derived from dihydroxybiphenyl are preferred.
  • repeating unit containing 2,6-naphthylene group in liquid crystal polyester that is, repeating unit (1) in which Ar 1 is 2,6-naphthylene group, repeating unit in which Ar 2 is 2,6-naphthylene group (2) and the total content of the repeating unit (3) in which Ar 3 is a 2,6-naphthylene group is the total amount of all repeating units (the mass of each repeating unit constituting the liquid crystal polyester is expressed by the formula of each repeating unit)
  • the substance amount equivalent amount (mole) of each repeating unit is obtained, and the sum thereof is 40 mol% or more.
  • the content of 2,6-naphthylene groups is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 70 mol% or more.
  • the content of the repeating unit (1) is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, still more preferably 45 to 65 mol, based on the total amount of all repeating units.
  • the content of the repeating unit (2) is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, still more preferably 17.5 to 27.27%, based on the total amount of all repeating units.
  • the content of the repeating unit (3) is preferably from 10 to 35 mol%, more preferably from 15 to 30 mol%, still more preferably from 17.5 to mol based on the total amount of all repeating units. 27.5 mol%.
  • the liquid crystal polyester having such a predetermined repeating unit composition has an excellent balance between heat resistance and moldability.
  • the liquid crystalline polyester may have a repeating unit other than the repeating units (1) to (3) as necessary, but the content thereof is usually 10 moles relative to the total amount of all the repeating units. % Or less, preferably 5 mol% or less.
  • a typical example of a liquid crystalline polyester having high heat resistance and high melt tension is a repeating unit (1) in which Ar 1 is a 2,6-naphthylene group, that is, 6-hydroxy-2- with respect to the total amount of all repeating units.
  • the repeating unit derived from naphthoic acid is preferably 40 to 74.8 mol%, more preferably 40 to 64.5 mol%, still more preferably 50 to 58 mol%, and Ar 2 is a 2,6-naphthylene group.
  • the repeating unit (2) that is, the repeating unit derived from 2,6-naphthalenedicarboxylic acid is preferably 12.5 to 30 mol%, more preferably 17.5 to 30 mol%, and still more preferably 20 to 25 mol%.
  • repeating units Ar 2 is 1,4-phenylene group (2), i.e., repeating units derived from terephthalic acid, preferably 0.2 to 15 mol%, more preferably 0. To 12 mol%, more preferably having 2 to 10 mol%, the repeating units Ar 3 is 1,4-phenylene group (3), i.e., a repeating unit derived from hydroquinone, preferably 12.5 to 30 mol %, more preferably 17.5 to 30 mol%, more preferably having 20-25 mol%, and the content of the repeating unit (2) Ar 2 is 2,6-naphthylene group, Ar 2 is The total content of the repeating unit (2) which is a 2,6-naphthylene group and the repeating unit (2) wherein Ar 2 is a 1,4-phenylene group is preferably 0.5 mol times or more, more preferably It is 0.6 mol times or more.
  • the liquid crystalline polyester is a monomer that gives a repeating unit (1), that is, a predetermined aromatic hydroxycarboxylic acid, a monomer that gives a repeating unit (2), that is, a monomer that gives a predetermined aromatic dicarboxylic acid, and a repeating unit (3), That is, a predetermined aromatic diol is added to a total amount of monomers having 2,6-naphthylene groups, that is, a total amount of 6-hydroxy-2-naphthoic acid, 2,6-naphthalenedicarboxylic acid and 2,6-naphthalenediol.
  • the polymer can be produced by polymerization (polycondensation) so as to be 40 mol% or more based on the total amount of all monomers.
  • the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, and the aromatic diol may be independently replaced by a part or all of the polymerizable derivatives thereof.
  • polymerizable derivatives of a compound having a carboxyl group such as an aromatic hydroxycarboxylic acid and an aromatic dicarboxylic acid include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group, and a carboxyl group as a haloformyl.
  • a group formed by converting a carboxyl group into an acyloxycarbonyl group a group formed by converting a carboxyl group into an acyloxycarbonyl group.
  • polymerizable derivatives of hydroxyl group-containing compounds such as aromatic hydroxycarboxylic acids and aromatic diols include those obtained by acylating a hydroxyl group and converting it to an acyloxyl group.
  • the liquid crystalline polyester is preferably produced by melt polymerizing monomers and solid-phase polymerizing the obtained polymer (prepolymer). Thereby, liquid crystalline polyester with high heat resistance and high melt tension can be manufactured with good operability.
  • Melt polymerization may be carried out in the presence of a catalyst.
  • this catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, Nitrogen-containing heterocyclic compounds such as N, N-dimethylaminopyridine and N-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.
  • the liquid crystal polyester having the predetermined repeating unit composition thus obtained is excellent in water vapor barrier properties.
  • the liquid crystal polyester has a flow start temperature of preferably 280 ° C. or higher, more preferably 290 ° C. or higher, further preferably 295 ° C. or higher, and is usually 380 ° C. or lower, preferably 350 ° C. or lower.
  • a flow start temperature preferably 280 ° C. or higher, more preferably 290 ° C. or higher, further preferably 295 ° C. or higher, and is usually 380 ° C. or lower, preferably 350 ° C. or lower.
  • the flow start temperature is higher, the heat resistance and melt tension are more likely to be improved. However, if the flow start temperature is too high, a high temperature is required for melting, and thermal deterioration tends to occur during molding.
  • the flow start temperature is also called flow temperature or flow temperature, and is 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ) using a capillary rheometer having a nozzle with an inner diameter of 1 mm and a length of 10 mm.
  • This is a temperature at which the melt viscosity shows 4800 Pa ⁇ s (48,000 poise) when the heated melt of the liquid crystal polyester is extruded from the nozzle at a temperature rising rate of 5 ° C., which is a measure of the molecular weight of the liquid crystal polyester (See Naoyuki, “Liquid Crystal Polymers—Synthesis / Molding / Applications”, CMC Corporation, June 5, 1987, p. 95).
  • the liquid crystal polyester in the present invention preferably has a water vapor transmission rate measured at a temperature of 40 ° C. and a relative humidity of 90% when formed into a film having a thickness of 50 ⁇ m, preferably 0.05 g / m 2 ⁇ 24 h or less, More preferably, it is 0.01 g / m ⁇ 2 > * 24h or less, More preferably, it is 0.005 g / m ⁇ 2 > * 24h or less.
  • the liquid crystal polyester may be blended with other components as necessary to form a composition.
  • other components include fillers, thermoplastic resins other than liquid crystal polyesters, and additives.
  • the ratio of the liquid crystal polyester in the entire composition is preferably 80% by mass or more, and more preferably 90% by mass or more.
  • fillers include glass fibers such as milled glass fibers and chopped glass fibers, potassium titanate whiskers, alumina whiskers, aluminum borate whiskers, silicon carbide whiskers, silicon nitride whiskers, and other metal or non-metallic whiskers.
  • glass fiber, mica, talc and carbon fiber are preferably used.
  • the filler may be surface-treated as necessary, and examples of the surface treatment agent include reactivity such as a silane coupling agent, a titanate coupling agent, and a borane coupling agent.
  • examples of the surface treatment agent include reactivity such as a silane coupling agent, a titanate coupling agent, and a borane coupling agent.
  • Examples include coupling agents and lubricants such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants.
  • thermoplastic resins other than liquid crystal polyester include polycarbonate, polyamide, polysulfone, polyphenylene sulfide, polyphenylene ether, polyether ketone, and polyetherimide resin.
  • additives include mold release improvers such as fluororesins and metal soaps, nucleating agents, antioxidants, stabilizers, plasticizers, lubricants, anti-coloring agents, coloring agents, ultraviolet absorbers, antistatic agents, Examples include lubricants and flame retardants.
  • a liquid crystalline polyester film that becomes the liquid crystalline polyester layer of the laminated sheet of the present invention can be obtained.
  • the film forming method include an extrusion molding method, a press molding method, a solution casting method, and an injection molding method, and the extrusion molding method is preferable.
  • the extrusion molding method include a T-die method and an inflation method. In the T-die method, uniaxial stretching or biaxial stretching may be performed.
  • the draw ratio (draft ratio) of the uniaxially stretched film is usually 1.1 to 40, preferably 10 to 40, more preferably 15 to 35.
  • the stretch ratio in the MD direction (extrusion direction) of the biaxial film is usually 1.2 to 40 times, and the stretch ratio in the TD direction (direction perpendicular to the extrusion direction) of the biaxial film is usually 1.2 to 20 times. Is double.
  • the thickness of the liquid crystal polyester film is preferably 5 to 100 ⁇ m, more preferably 10 to 75 ⁇ m, and further preferably 15 to 75 ⁇ m. If it is too thin, the strength will be insufficient, and if it is too thick, the flexibility will be insufficient.
  • the liquid crystal polyester film thus obtained has excellent water vapor barrier properties, and the water vapor permeability measured at a temperature of 40 ° C. and a relative humidity of 90% is preferably 0.05 g / m 2 ⁇ 24 h or less, more preferably 0. 0.01 g / m 2 ⁇ 24 h or less, more preferably 0.005 g / m 2 ⁇ 24 h or less.
  • the liquid crystal polyester film may be provided with a water vapor barrier layer or another functional layer to further improve the water vapor barrier property, and may be a laminated film. Further, a plurality of liquid crystal polyester films may be laminated or laminated with other resin films to be used as a laminated film.
  • the laminated sheet of the present invention having a graphite layer and a liquid crystal polyester layer can be obtained by joining the liquid crystal polyester film thus obtained to a graphite sheet.
  • the liquid crystal polyester film may be bonded to only one surface of the graphite sheet, or may be bonded to both surfaces of the graph fight sheet.
  • the liquid crystal polyester film is bonded to only one surface of the graphite sheet, it is preferable to use the bonded surface toward the front side that easily comes into contact with air.
  • the graphite sheet is used after being patterned into a predetermined shape by punching or the like according to the use of the laminated sheet.
  • the laminated sheet is used for a planar heating element or a heat radiating sheet, it is preferable that the graphite sheet is patterned so that electricity and heat are distributed to the front surface as much as possible.
  • a terminal for energization is provided, and when the laminated sheet is used as a heat radiating sheet, a terminal for removing static electricity is usually provided.
  • the planar heating element using the laminated sheet of the present invention is used as, for example, a heating element for fixing toner in a printer or a copying machine, or a heating element for heat retention of a measuring instrument or a motor.
  • seat formed using the laminated sheet of this invention is used as a thermal radiation sheet for printed wiring boards, for example.
  • Production Example 2 In the same reactor as in Production Example 1, 911 g (6.6 mol) of p-hydroxybenzoic acid, 274 g (1.65 mol) of terephthalic acid, 91 g (0.55 mol) of isophthalic acid, 4,4′-dihydroxybiphenyl 409 g (2.2 mol), 1235 g of acetic anhydride (12.1 mol), and 0.17 g of 1-methylimidazole as a catalyst were added, and the gas in the reactor was replaced with nitrogen gas, followed by stirring under a nitrogen gas stream While raising the temperature from room temperature to 150 ° C. over 15 minutes, the mixture was refluxed at 150 ° C. for 1 hour.
  • the mixture was cooled to obtain a powdery liquid crystal polyester.
  • this liquid crystal polyester 60 mol% of the repeating unit (1) in which Ar 1 is a 1,4-phenylene group, 15 mol% of the repeating unit (2) in which Ar 2 is a 1,4-phenylene group, and Ar 2 is 5% by mole of the repeating unit (2) which is a 1,3-phenylene group and 20% of the repeating unit (3) whose Ar 3 is a 4,4′-biphenylylene group, and its flow initiation temperature is 327 ° C. there were.
  • Example 1 The liquid crystalline polyester obtained in Production Example 1 was granulated with a twin-screw extruder ("PCM-30" by Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted, extruded from a T die (lip length: 300 mm, lip clearance: 1 mm, die temperature: 350 ° C.) and cooled to obtain a liquid crystal polyester film having a thickness of 25 ⁇ m.
  • PCM-30 twin-screw extruder
  • the liquid crystal polyester film has a water vapor permeability of 0.011 g / m 2 ⁇ 24 h, and a laminated sheet having a graphite layer and a liquid crystal polyester layer obtained by joining the liquid crystal polyester film to the graphite sheet is a liquid crystal polyester.
  • the layer has excellent water vapor barrier properties.
  • Example 2 The liquid crystalline polyester obtained in Production Example 1 was granulated with a twin-screw extruder ("PCM-30" by Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted and extruded from a T die (lip length 300 mm, lip clearance 1 mm, die temperature 350 ° C.) into a film and cooled to obtain a liquid crystal polyester film having a thickness of 50 ⁇ m.
  • PCM-30 twin-screw extruder
  • the liquid crystal polyester film has a water vapor permeability of 0.003 g / m 2 ⁇ 24 h, and a laminated sheet having a graphite layer and a liquid crystal polyester layer obtained by joining the liquid crystal polyester film to the graphite sheet is a liquid crystal polyester.
  • the layer has excellent water vapor barrier properties.
  • Comparative Example 1 The liquid crystalline polyester obtained in Production Example 2 was granulated with a twin-screw extruder ("PCM-30" from Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted, extruded from a T die (lip length: 300 mm, lip clearance: 1 mm, die temperature: 350 ° C.) and cooled to obtain a liquid crystal polyester film having a thickness of 25 ⁇ m.
  • PCM-30 twin-screw extruder
  • the liquid crystal polyester film has a water vapor permeability of 0.343 g / m 2 ⁇ 24 h, and a laminated sheet having a graphite layer and a liquid crystal polyester layer obtained by joining the liquid crystal polyester film to a graphite sheet is a liquid crystal polyester.
  • the water vapor barrier property of the layer is insufficient.
  • Comparative Example 2 The liquid crystalline polyester obtained in Production Example 2 was granulated with a twin-screw extruder ("PCM-30" from Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted and extruded from a T die (lip length 300 mm, lip clearance 1 mm, die temperature 350 ° C.) into a film and cooled to obtain a liquid crystal polyester film having a thickness of 50 ⁇ m.
  • PCM-30 twin-screw extruder
  • the liquid crystal polyester film has a water vapor permeability of 0.080 g / m 2 ⁇ 24 h, and a laminated sheet having a graphite layer and a liquid crystal polyester layer obtained by joining the liquid crystal polyester film to the graphite sheet is a liquid crystal polyester.
  • the water vapor barrier property of the layer is insufficient.

Abstract

La présente invention concerne une feuille stratifiée comprenant une couche de graphite et une couche de polyester à cristaux liquides présentant d'excellentes propriétés de barrière contre la vapeur d'eau. Une feuille stratifiée selon la présente invention comprend une couche de graphite et une couche de polyester à cristaux liquides disposée sur au moins une surface de la couche de graphite, la couche de polyester à cristaux liquides étant une couche constituée d'un polyester à cristaux liquides doté d'unités répétitives représentées par les formules (1) à (3) et dans lequel la teneur d'une unité répétitive contenant un groupe 2,6-naphthylène est d'au moins 40% mol. par rapport à la teneur totale de toutes les unités répétitives. -O-Ar1-CO- (1)　-CO-Ar2-CO- (2)　-O-Ar3-O- (3) (Ar1, Ar2 et Ar3 dénotent chacun un groupe 2,6-naphthylène, un groupe 1,4-phénylène, un groupe 4,4'-biphénylylène ou similaire).
PCT/JP2012/051920 2011-01-31 2012-01-30 Feuille stratifiée et son utilisation WO2012105468A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2004090445A (ja) * 2002-08-30 2004-03-25 Taisei Laminator Co Ltd カーボングラファイトシート
JP2006134672A (ja) * 2004-11-04 2006-05-25 Taisei Laminator Co Ltd 面状発熱体、および面状発熱体を用いた発熱ブロック
JP2006188022A (ja) * 2005-01-07 2006-07-20 Taisei Laminator Co Ltd カーボングラファイトシート
JP2010135782A (ja) * 2008-11-10 2010-06-17 Sumitomo Chemical Co Ltd 太陽電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004090445A (ja) * 2002-08-30 2004-03-25 Taisei Laminator Co Ltd カーボングラファイトシート
JP2006134672A (ja) * 2004-11-04 2006-05-25 Taisei Laminator Co Ltd 面状発熱体、および面状発熱体を用いた発熱ブロック
JP2006188022A (ja) * 2005-01-07 2006-07-20 Taisei Laminator Co Ltd カーボングラファイトシート
JP2010135782A (ja) * 2008-11-10 2010-06-17 Sumitomo Chemical Co Ltd 太陽電池

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