WO2012111662A1 - Organic electroluminescent substrate, and organic electroluminescent element - Google Patents

Organic electroluminescent substrate, and organic electroluminescent element Download PDF

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Publication number
WO2012111662A1
WO2012111662A1 PCT/JP2012/053387 JP2012053387W WO2012111662A1 WO 2012111662 A1 WO2012111662 A1 WO 2012111662A1 JP 2012053387 W JP2012053387 W JP 2012053387W WO 2012111662 A1 WO2012111662 A1 WO 2012111662A1
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layer
organic
group
liquid crystal
crystal polyester
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PCT/JP2012/053387
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French (fr)
Japanese (ja)
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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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Priority to KR1020137024421A priority Critical patent/KR20140009360A/en
Publication of WO2012111662A1 publication Critical patent/WO2012111662A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/351—Thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to an organic EL (electroluminescence) substrate having a liquid crystal polyester layer.
  • the present invention also relates to an organic EL element using this organic EL substrate.
  • the organic EL element usually has a structure in which a pair of electrodes is disposed on a substrate and an organic EL layer is disposed between the pair of electrodes.
  • An example thereof is shown in FIG.
  • the cathode 4A, the organic EL layer 5 and the anode 4B are disposed in this order on the substrate 1, and the sealing layer 6 is further disposed on the cathode 4A, the peripheral edge between the substrate 1 and the sealing layer 6.
  • the part is sealed with a sealing material 3.
  • the organic EL layer 5 includes a light emitting layer 5b, an electron transport layer 5a disposed on the cathode 4A side, and a hole transport layer 5c disposed on the anode 4B side.
  • Patent Document 1 discloses 4,4′-dihydroxybiphenyl as a liquid crystal polyester constituting the liquid crystal polyester film.
  • a repeating unit derived from p-aminophenol Those having a repeating unit derived from Refutaru acid is disclosed.
  • the conventional organic EL substrate having a liquid crystal polyester layer as disclosed in Patent Document 1 does not necessarily have sufficient weather resistance, for example, when it is irradiated with light from the back side for a long time due to reflected light, it is warped and peeled off, It may be torn. Accordingly, an object of the present invention is to provide an organic EL substrate having a liquid crystal polyester layer and excellent weather resistance.
  • the present invention provides an organic EL substrate in which a white pigment-containing layer is provided on the back side of a liquid crystal polyester layer.
  • the present invention also provides an organic EL device comprising the organic EL substrate, a pair of electrodes disposed on the organic EL substrate, and an organic EL layer disposed between the pair of electrodes.
  • the organic EL substrate of the present invention is excellent in weather resistance.
  • the organic EL substrate of the present invention has a white pigment-containing layer 26 provided on the back side (surface opposite to the light emitting surface) of the liquid crystal polyester layer 23 as shown in FIG.
  • the liquid crystalline polyester constituting the liquid crystalline polyester layer 23 is a liquid crystalline polyester that exhibits liquid crystallinity in a molten state, and is preferably melted at a temperature of 450 ° C. or lower.
  • the liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide.
  • the liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.
  • a typical example of the liquid crystal polyester is polymerization (polycondensation) of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine. At least one compound selected from the group consisting of aromatic dicarboxylic acids and aromatic diols, aromatic hydroxyamines and aromatic diamines, And those obtained by polymerizing a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid.
  • the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine, and the aromatic diamine are each independently replaced with a part or all of the polymerizable derivative. Also good.
  • Examples of 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 the carboxyl group as a haloformyl. And those obtained by converting a carboxyl group into an acyloxycarbonyl group.
  • Examples of polymerizable derivatives of hydroxyl group-containing compounds such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating a hydroxyl group and converting it to an acyloxyl group.
  • Examples of the polymerizable derivative of a compound having an amino group such as aromatic hydroxyamine and aromatic diamine include those obtained by acylating an amino group and converting it to an acylamino group.
  • repeating unit (1) As the liquid crystalline polyester, since it has excellent water vapor barrier properties, a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as repeating unit (1)) and a repeating unit represented by the following formula (2): Those having a repeating unit (hereinafter sometimes referred to as repeating unit (2)) and a repeating unit represented by the following formula (3) (hereinafter sometimes referred to as repeating unit (3)) are preferably used.
  • 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.
  • polymerizable derivatives thereof instead of some or all of the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid and aromatic diol, polymerizable derivatives thereof may be used.
  • polymerizable derivatives of compounds having a carboxyl group such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group, and a carboxyl group as a haloformyl. And 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
  • 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 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 rate of temperature rise, and is a measure of the molecular weight of the liquid crystal polyester (Naoyuki Koide) Ed., “Liquid Crystal Polymers—Synthesis / Molding / Application—”, CMC Corporation, June 5, 1987, p. 95).
  • the liquid crystal polyester 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% when formed into a film having a thickness of 50 ⁇ m is usually 0.1 g / m 2. 24h or less, preferably 0.05 g / m 2 ⁇ 24h or less, more preferably 0.01 g / m 2 ⁇ 24h or less, more preferably less than or equal to 0.005g / m 2 ⁇ 24h.
  • 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.
  • the blending amount of the filler is usually 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester.
  • 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 crystal polyester film to be the liquid crystal polyester layer 23 of the organic EL substrate of the present invention can be obtained by forming the liquid crystal polyester thus obtained or a composition thereof into a film.
  • 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 layer 23 is preferably 5 to 500 ⁇ m, more preferably 10 to 250 ⁇ m, and further preferably 15 to 200 ⁇ 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 layer 23 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 usually 0.1 g / m 2 ⁇ 24 h or less, preferably 0.05 g / m. 2 ⁇ 24h or less, more preferably 0.01g / m 2 ⁇ 24h or less, more preferably less than or equal to 0.005g / m 2 ⁇ 24h.
  • the liquid crystal polyester layer 23 may be provided with a water vapor barrier layer 24 on at least one surface thereof. That is, the liquid crystal polyester film to be the liquid crystal polyester layer 23 may be a laminated film by providing the water vapor barrier layer 24 on at least one surface thereof. In the example of FIG. 2, the water vapor barrier layer 24 is provided on the back side of the liquid crystal polyester layer 23, but may be provided on the front side of the liquid crystal polyester layer 23, and the front side and back side of the liquid crystal polyester layer 23 May be provided.
  • Substances constituting the water vapor barrier layer 24 include at least one element selected from the group consisting of aluminum, silicon, titanium, chromium, iron, cobalt, nickel, copper, zinc, silver and gold, oxide, and nitridation. And oxynitrides are preferable, and two or more of them may be used as necessary.
  • Examples of the method for forming the water vapor barrier layer 24 include PVD methods such as vapor deposition, sputtering, and ion plating, CVD methods such as plasma CVD, thermal CVD, and laser CVD, sol-gel methods, and plating. And wet methods such as coating method and coating method. Further, a foil prepared or obtained separately may be bonded to the liquid crystal polyester film.
  • the thickness of the water vapor barrier layer 24 is preferably 5 to 250 nm, more preferably 40 to 100 nm. If it is too thin, the water vapor barrier property will be insufficient, and if it is too thick, the flexibility will be insufficient.
  • the laminate of the liquid crystal polyester layer 23 and the water vapor barrier layer 24 thus configured 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 usually 0.005 g / m 2 ⁇ 24h or less, preferably 0.001g / m 2 ⁇ 24h or less, more preferably 0.0005g / m 2 ⁇ 24h or less, more preferably less than or equal to 0.0001g / m 2 ⁇ 24h.
  • a white pigment-containing layer 26 is provided on the back side of the liquid crystal polyester layer 23. Thereby, the organic EL substrate 2 excellent in weather resistance can be obtained.
  • the white pigment-containing layer 26 is provided via the adhesive layer 25, but the white pigment-containing layer 26 may be provided by thermal fusion, for example, without using the adhesive layer 25. Good.
  • White pigments contained in the white pigment-containing layer 26 include basic lead carbonate (2PbCO 3 ⁇ Pb (OH) 2 (lead white), etc.), basic lead sulfate (2PbSO 4 ⁇ Pb (OH) 2 etc.), base Lead silicate (Pb 2 SiO 4 ⁇ Pb (OH) 2 etc.), zinc white (ZnO (zinc oxide)), zinc sulfide, lithopone (mixture of zinc sulfide and barium sulfate), antimony trioxide and titanium oxide Preferably, two or more of them may be used as necessary.
  • the white pigment-containing layer 26 is preferably provided using a resin film containing a white pigment, and the resin film, that is, the resin contained in the white pigment-containing layer 26 is preferably a polyester such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the content of the white pigment in the white pigment-containing layer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on the total amount of the white pigment-containing layer.
  • the thickness of the white pigment-containing layer 56 is preferably 5 to 500 ⁇ m, more preferably 10 to 400 ⁇ m.
  • the liquid crystal polyester layer 23 may be provided on the front side with another resin layer, preferably a polyolefin layer 21, in order to impart design properties.
  • the polyolefin layer 21 is provided via the adhesive layer 22, but the polyolefin layer 21 may be provided by, for example, thermal fusion without using the adhesive layer 22.
  • the polyolefin constituting the polyolefin layer 21 is preferably polyethylene, more preferably low density polyethylene (LDPE), and still more preferably linear low density polyethylene (LLDPE).
  • the polyolefin layer 21 is preferably provided using a polyolefin film.
  • a desired color pigment or dye may be included in the polyolefin film, that is, the polyolefin layer 21.
  • the thickness of the polyolefin layer 21 is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
  • the organic EL substrate of the present invention thus obtained has a pair of electrodes 4A and 4B disposed thereon, and the organic EL layer 5 is disposed between the pair of electrodes 4A and 4B.
  • the organic EL substrate 2 when the organic EL substrate 2 has the water vapor barrier layer 24 only on one surface of the liquid crystal polyester layer 23, it is opposite to the surface of the liquid crystal polyester layer 23 on which the water vapor barrier layer 24 is disposed. It is preferable to arrange a pair of electrodes 4A and 4B and an organic EL layer 5 on the side surface.
  • the cathode 4A, the organic EL layer 5 and the anode 4B are arranged in this order on the organic EL substrate 2, but the anode 4B and the organic EL layer 5 are arranged on the organic EL substrate 2. And the cathode 4A may be arranged in this order.
  • the organic EL layer 5 is comprised from the light emitting layer 5b, the electron carrying layer 5a arrange
  • a light emitting layer / electron transport layer having both functions may be provided, or in place of the issue layer 5b and the hole transport layer 5c, both functions may be provided. You may have a light emitting layer and hole transport layer provided.
  • the material of the light emitting layer 5b may be a polymer type or a low molecular type.
  • the materials of the cathode 4A and the anode 4B may be independently metals such as aluminum and copper, or may be metal oxides such as indium tin oxide and zinc tin oxide, but the light emitting layer 5b. In order to transmit the light emitted from, at least one of them is required to be transparent. Since the organic EL substrate 2 of the present invention has a liquid crystal polyester layer and is usually inferior in transparency, the organic EL element 1 using this layer as a substrate is opposite to the organic EL substrate 2 from the light emitting layer 5b. It is preferable that the top emission type emit light in the direction.
  • the organic EL element 1 is a top emission type
  • transparency is calculated
  • the sealing layer 6 disposed on the substrate is also required to have transparency.
  • the sealing layer 6 is preferably a glass plate in terms of water vapor barrier properties, but is preferably a resin film in terms of flexibility.
  • an ultraviolet curable resin is preferably used.
  • a pair of electrodes and the organic EL layer may be covered with a sealing material such as an ultraviolet curable resin without using a plate-like member such as a glass plate or a resin film.
  • the organic EL device thus obtained uses the organic EL substrate of the present invention having excellent weather resistance as the substrate, for example, even if it is irradiated with light from the back side for a long time by reflected light, it is difficult to warp and peel off. It ’s hard to break.
  • Production Example 1 (1) To a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 103.499 g (5.5 mol) of 6-hydroxy-2-naphthoic acid, 378 of 2,6-naphthalenedicarboxylic acid 378 0.33 g (1.75 mol), 83.07 g (0.5 mol) of terephthalic acid, 272.52 g of hydroquinone (2.475 mol: 0.225 based on the total amount of 2,6-naphthalenedicarboxylic acid and terephthalic acid) Molar excess), 1226.87 g (12 moles) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst, and after replacing the gas in the reactor with nitrogen gas, stirring at room temperature under a nitrogen gas stream To 145 ° C.
  • Production Example 2 (1) In the same reactor as in Production Example 1, 911 g (6.6 mol) of p-hydroxybenzoic acid, 91 g (0.55 mol) of isophthalic acid, 274 g (1.65 mol) of terephthalic 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.
  • Production Example 1 (2) The liquid crystalline polyester obtained in Production Example 1 (1) was granulated with a twin-screw extruder (“PCM-30” from Ikegai Co., Ltd.), pelletized, and then put into a single-screw extruder (screw diameter 50 mm). It was supplied and melted, 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 having a thickness of 50 ⁇ m. The water vapor permeability of this liquid crystal polyester film was 0.0030 g / m 2 ⁇ 24 h.
  • PCM-30 twin-screw extruder
  • Production Example 2 (2) The liquid crystalline polyester obtained in Production Example 2 (1) was granulated with a twin screw extruder ("PCM-30" by Ikegai Co., Ltd.), pelletized, and then put into a single screw extruder (screw diameter 50 mm). It was supplied and melted, 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 having a thickness of 50 ⁇ m. The water vapor permeability of this liquid crystal polyester film was 0.080 g / m 2 ⁇ 24 h.
  • PCM-30 twin screw extruder
  • Production Example 1 (3) An aluminum oxide thin film having a thickness of 20 nm was formed as a gas barrier layer on one side of the liquid crystal polyester film obtained in Production Example 1 (2) to obtain a laminated film.
  • the water vapor permeability of this laminated film was less than 0.0001 g / m 2 ⁇ 24 h (less than the detection lower limit).
  • Production Example 2 (3) An aluminum oxide thin film having a thickness of 20 nm was formed as a gas barrier layer on one side of the liquid crystal polyester film obtained in Production Example 2 (2) to obtain a laminated film.
  • the water vapor permeability of this laminated film was 0.0020 g / m 2 ⁇ 24 h.
  • a urethane adhesive Mitsubishi Chemical Co., Ltd .: main agent “Takelac A511” / curing agent “A50
  • urethane adhesive Mitsubishi Chemical Co., Ltd .: main agent “Takelac A511” / curing agent “A50”
  • Tolu Co., Ltd. “Lumirror E20”: containing titanium oxide) 10/1 (mass ratio)
  • SYMBOLS 1 ... Organic EL element, 2 ... Substrate, 3 ... Sealing material, 4A ... Cathode, 4B ... Anode, 5 ... Organic EL layer, 5a ... Electron transport layer, 5b ... light emitting layer, 5c ... hole transport layer, 6 ... sealing layer, 21 ... polyolefin layer, 22 ... adhesive layer, 23 ... liquid crystal polyester layer, 24 ... Water vapor barrier layer, 25 ... adhesive layer, 26 ... white pigment-containing layer.

Abstract

The present invention addresses the problem of providing an organic electroluminescent substrate exhibiting superior weather resistance. The present invention relates to an organic electroluminescent substrate formed by providing the underside of a liquid crystal polyester layer with a layer containing a white pigment. The liquid crystal polyester layer is preferably a layer formed from a liquid crystal polyester having a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a repeating unit represented by formula (3); wherein the ratio of the content of the repeating units containing a 2, 6-naphthylene group to the total amount of all of the repeating units is at least 40mol%. (1) - O - Ar1 - CO - (2) - CO - Ar2 - CO - (3) - O - Ar3 - O - (Ar1 represents a 2, 6-naphthylene group, a 1, 4-phenylene group, or a 4, 4'-biphenylene group. Ar2 and Ar3 independently represent a 2, 6-naphthylene group, a 1, 4-phenylene group, a 1, 3-phenylene group, or a 4, 4'-biphenylene group.)

Description

有機ＥＬ用基板及び有機ＥＬ素子Organic EL substrate and organic EL element
　本発明は、液晶ポリエステル層を有する有機ＥＬ（エレクトロルミネッセンス）用基板に関する。また、本発明は、この有機ＥＬ用基板を用いてなる有機ＥＬ素子に関する。 The present invention relates to an organic EL (electroluminescence) substrate having a liquid crystal polyester layer. The present invention also relates to an organic EL element using this organic EL substrate.
　有機ＥＬ素子は、通常、基板の上に一対の電極が配置され、この一対の電極間に有機ＥＬ層が配置されてなる構造を有しており、図１にその例を示す。この例では、基板１の上に、陰極４Ａ、有機ＥＬ層５及び陽極４Ｂがこの順に配置され、さらにその上に封止層６が配置され、基板１と封止層６との間の周縁部が封止材３で封止されている。また、有機ＥＬ層５は、発光層５ｂと、その陰極４Ａ側に配置された電子輸送層５ａと、その陽極４Ｂ側に配置された正孔輸送層５ｃとから構成されている。 The organic EL element usually has a structure in which a pair of electrodes is disposed on a substrate and an organic EL layer is disposed between the pair of electrodes. An example thereof is shown in FIG. In this example, the cathode 4A, the organic EL layer 5 and the anode 4B are disposed in this order on the substrate 1, and the sealing layer 6 is further disposed on the cathode 4A, the peripheral edge between the substrate 1 and the sealing layer 6. The part is sealed with a sealing material 3. The organic EL layer 5 includes a light emitting layer 5b, an electron transport layer 5a disposed on the cathode 4A side, and a hole transport layer 5c disposed on the anode 4B side.
　基板１としては、通常、ガラス板が用いられるが、フレキシブル性に乏しため、有機ＥＬ素子の連続生産が困難であり、また、衝撃に弱く、重いという欠点がある。そこで、基板１として樹脂フィルムを用いることが検討されているが、一般的な樹脂フィルムは、水蒸気バリア性や寸法安定性が低いという問題がある。このような問題を解決するため、基板１として液晶ポリエステルフィルムを用いることが検討されており、例えば、特許文献１には、前記液晶ポリエステルフィルムを構成する液晶ポリエステルとして、４，４’－ジヒドロキシビフェニルに由来する繰返し単位とフタル酸に由来する繰返し単位とｐ－ヒドロキシ安息香酸に由来する繰返し単位とを有するものや、６－ヒドロキシ－２－ナフトエ酸に由来する繰返し単位とｐ－ヒドロキシ安息香酸に由来する繰返し単位とを有するものや、エチレングリコールに由来する繰返し単位とテレフタル酸に由来する繰返し単位とｐ－ヒドロキシ安息香酸に由来する繰返し単位とを有するものや、６－ヒドロキシ－２－ナフトエ酸に由来する繰返し単位とｐ－アミノフェノールに由来する繰返し単位とテレフタル酸に由来する繰返し単位とを有するものが、開示されている。 As the substrate 1, a glass plate is usually used. However, since it is poor in flexibility, it is difficult to continuously produce organic EL elements, and it is weak against impact and heavy. Then, although using a resin film as the board | substrate 1 is examined, a general resin film has the problem that water vapor | steam barrier property and dimensional stability are low. In order to solve such problems, the use of a liquid crystal polyester film as the substrate 1 has been studied. For example, Patent Document 1 discloses 4,4′-dihydroxybiphenyl as a liquid crystal polyester constituting the liquid crystal polyester film. A repeating unit derived from phthalic acid, a repeating unit derived from phthalic acid and a repeating unit derived from p-hydroxybenzoic acid, a repeating unit derived from 6-hydroxy-2-naphthoic acid, and p-hydroxybenzoic acid. A repeating unit derived from ethylene glycol, a repeating unit derived from ethylene glycol, a repeating unit derived from terephthalic acid, and a repeating unit derived from p-hydroxybenzoic acid, or 6-hydroxy-2-naphthoic acid And a repeating unit derived from p-aminophenol Those having a repeating unit derived from Refutaru acid is disclosed.
特開２００９－３２４６４号公報JP 2009-32464 A
　特許文献１に開示の如き液晶ポリエステル層を有する従来の有機ＥＬ用基板は、耐候性が必ずしも十分でなく、例えば、反射光により裏側から長期間にわたり光照射を受けると、反って、剥がれたり、破れたりすることがある。そこで、本発明の目的は、液晶ポリエステル層を有し、耐候性に優れる有機ＥＬ用基板を提供することにある。 The conventional organic EL substrate having a liquid crystal polyester layer as disclosed in Patent Document 1 does not necessarily have sufficient weather resistance, for example, when it is irradiated with light from the back side for a long time due to reflected light, it is warped and peeled off, It may be torn. Accordingly, an object of the present invention is to provide an organic EL substrate having a liquid crystal polyester layer and excellent weather resistance.
　前記目的を達成するため、本発明は、液晶ポリエステル層の裏側に、白色顔料含有層が設けられてなる有機ＥＬ用基板を提供する。 In order to achieve the object, the present invention provides an organic EL substrate in which a white pigment-containing layer is provided on the back side of a liquid crystal polyester layer.
　また、本発明は、前記有機ＥＬ用基板と、前記有機ＥＬ用基板上に配置された一対の電極と、前記一対の電極間に配置された有機ＥＬ層とを有する有機ＥＬ素子を提供する。 The present invention also provides an organic EL device comprising the organic EL substrate, a pair of electrodes disposed on the organic EL substrate, and an organic EL layer disposed between the pair of electrodes.
　本発明の有機ＥＬ用基板は、耐候性に優れている。 The organic EL substrate of the present invention is excellent in weather resistance.
有機ＥＬ素子の例を模式的に示す断面図である。It is sectional drawing which shows the example of an organic EL element typically. 本発明の有機ＥＬ基板の例を模式的に示す断面図である。It is sectional drawing which shows the example of the organic electroluminescent board | substrate of this invention typically.
　本発明の有機ＥＬ用基板は、図２に示す如く、液晶ポリエステル層２３の裏側（発光面とは反対の面側）に、白色顔料含有層２６が設けられてなるものである。 The organic EL substrate of the present invention has a white pigment-containing layer 26 provided on the back side (surface opposite to the light emitting surface) of the liquid crystal polyester layer 23 as shown in FIG.
　液晶ポリエステル層２３を構成する液晶ポリエステルは、溶融状態で液晶性を示す液晶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。なお、液晶ポリエステルは、液晶ポリエステルアミドであってもよいし、液晶ポリエステルエーテルであってもよいし、液晶ポリエステルカーボネートであってもよいし、液晶ポリエステルイミドであってもよい。液晶ポリエステルは、原料モノマーとして芳香族化合物のみを用いてな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 crystalline polyester constituting the liquid crystalline polyester layer 23 is a liquid crystalline polyester that exhibits liquid crystallinity in a molten state, and is preferably melted at a temperature of 450 ° C. or lower. The liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide. The liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.
　液晶ポリエステルの典型的な例としては、芳香族ヒドロキシカルボン酸と芳香族ジカルボン酸と芳香族ジオール、芳香族ヒドロキシアミン及び芳香族ジアミンからなる群から選ばれる少なくとも１種の化合物とを重合（重縮合）させてなるもの、複数種の芳香族ヒドロキシカルボン酸を重合させてなるもの、芳香族ジカルボン酸と芳香族ジオール、芳香族ヒドロキシアミン及び芳香族ジアミンからなる群から選ばれる少なくとも１種の化合物とを重合させてなるもの、及びポリエチレンテレフタレート等のポリエステルと芳香族ヒドロキシカルボン酸とを重合させてなるものが挙げられる。ここで、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、芳香族ヒドロキシアミン及び芳香族ジアミンは、それぞれ独立に、その一部又は全部に代えて、その重合可能な誘導体が用いられてもよい。 A typical example of the liquid crystal polyester is polymerization (polycondensation) of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine. At least one compound selected from the group consisting of aromatic dicarboxylic acids and aromatic diols, aromatic hydroxyamines and aromatic diamines, And those obtained by polymerizing a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid. Here, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine, and the aromatic diamine are each independently replaced with a part or all of the polymerizable derivative. Also good.
　芳香族ヒドロキシカルボン酸及び芳香族ジカルボン酸のようなカルボキシル基を有する化合物の重合可能な誘導体の例としては、カルボキシル基をアルコキシカルボニル基又はアリールオキシカルボニル基に変換してなるもの、カルボキシル基をハロホルミル基に変換してなるもの、及びカルボキシル基をアシルオキシカルボニル基に変換してなるものが挙げられる。芳香族ヒドロキシカルボン酸、芳香族ジオール及び芳香族ヒドロキシアミンのようなヒドロキシル基を有する化合物の重合可能な誘導体の例としては、ヒドロキシル基をアシル化してアシルオキシル基に変換してなるものが挙げられる。芳香族ヒドロキシアミン及び芳香族ジアミンのようなアミノ基を有する化合物の重合可能な誘導体の例としては、アミノ基をアシル化してアシルアミノ基に変換してなるものが挙げられる。 Examples of 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 the carboxyl group as a haloformyl. And those obtained by converting a carboxyl group into an acyloxycarbonyl group. Examples of polymerizable derivatives of hydroxyl group-containing compounds such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating a hydroxyl group and converting it to an acyloxyl group. . Examples of the polymerizable derivative of a compound having an amino group such as aromatic hydroxyamine and aromatic diamine include those obtained by acylating an amino group and converting it to an acylamino group.
　液晶ポリエステルとしては、水蒸気バリア性に優れることから、下記式（１）で表される繰返し単位（以下、繰返し単位（１）ということがある）と、下記式（２）で表される繰返し単位（以下、繰返し単位（２）ということがある）と、下記式（３）で表される繰返し単位（以下、繰返し単位（３）ということがある）とを有するものが、好ましく用いられる。 As the liquid crystalline polyester, since it has excellent water vapor barrier properties, a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as repeating unit (1)) and a repeating unit represented by the following formula (2): Those having a repeating unit (hereinafter sometimes referred to as repeating unit (2)) and a repeating unit represented by the following formula (3) (hereinafter sometimes referred to as repeating unit (3)) are preferably used.
－Ｏ－Ａｒ1－ＣＯ－　　　　（１）
－ＣＯ－Ａｒ2－ＣＯ－　　　（２）
－Ｏ－Ａｒ3－Ｏ－　　　　　（３）
（Ａｒ1は、２，６－ナフチレン基、１，４－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ2及びＡｒ3は、それぞれ独立に、２，６－ナフチレン基、１，４－フェニレン基、１，３－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ1、Ａｒ2又はＡｒ3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。） —O—Ar 1 —CO— (1)
—CO—Ar 2 —CO— (2)
—O—Ar 3 —O— (3)
(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.)
　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が挙げられる。前記アルキル基の例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ヘキシル基、２－エチルヘキシル基、ｎ－オクチル基及びｎ－デシル基が挙げられ、その炭素数は、通常１～１０である。前記アリール基の例としては、フェニル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、１－ナフチル基及び２－ナフチル基が挙げられ、その炭素数は、通常６～２０である。前記水素原子がこれらの基で置換されている場合、その数は、Ａｒ1、Ａｒ2又はＡｒ3で表される前記基毎に、それぞれ独立に、通常２個以下であり、好ましくは１個以下である。 As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the alkyl group 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. Examples of the aryl group 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. . When 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.
　繰返し単位（１）は、所定の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。繰返し単位（１）としては、Ａｒ1が２，６－ナフチレン基であるもの、すなわち６－ヒドロキシ－２－ナフトエ酸に由来する繰返し単位が好ましい。 The repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid. As 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.
　繰返し単位（２）は、所定の芳香族ジカルボン酸に由来する繰返し単位である。繰返し単位（２）としては、Ａｒ2が２，６－ナフチレン基であるもの、すなわち２，６－ナフタレンジカルボン酸に由来する繰返し単位、及びＡｒ2が１，４－フェニレン基であるもの、すなわちテレフタル酸に由来する繰返し単位が好ましい。 The repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid. As the repeating unit (2), 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.
　繰返し単位（３）は、所定の芳香族ジオールに由来する繰返し単位である。繰返し単位（３）としては、Ａｒ3が１，４－フェニレン基であるもの、すなわちヒドロキノンに由来する繰返し単位、及びＡｒ3が４，４’－ビフェニリレン基であるもの、すなわち４，４’－ジヒドロキシビフェニルに由来する繰返し単位が好ましい。 The repeating unit (3) is a repeating unit derived from a predetermined aromatic diol. As the repeating unit (3), 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.
　液晶ポリエステル中、２，６－ナフチレン基を含む繰返し単位の含有量、すなわち、Ａｒ1が２，６－ナフチレン基である繰返し単位（１）、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）、及びＡｒ3が２，６－ナフチレン基である繰返し単位（３）の合計含有量は、全繰返し単位の合計量（液晶ポリエステルを構成する各繰返し単位の質量を各繰返し単位の式量で割ることにより、各繰返し単位の物質量相当量（モル）を求め、それらを合計した値）に対して、４０モル％以上である。これにより、液晶ポリエステル層の水蒸気バリア性を高めることができる。この２，６－ナフチレン基の含有量は、好ましくは５０モル％以上、より好ましくは６０モル％以上、さらに好ましくは７０モル％以上である。 Content of 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) By dividing by the amount, the substance amount equivalent amount (mole) of each repeating unit is obtained, and the sum thereof is 40 mol% or more. Thereby, the water vapor | steam barrier property of a liquid-crystal polyester layer can be improved. 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.
　また、液晶ポリエステル中、繰返し単位（１）の含有量は、全繰返し単位の合計量に対して、好ましくは３０～８０モル％、より好ましくは４０～７０モル％、さらに好ましくは４５～６５モル％であり、繰返し単位（２）の含有量は、全繰返し単位の合計量に対して、好ましくは１０～３５モル％、より好ましくは１５～３０モル％、さらに好ましくは１７．５～２７．５モル％であり、繰返し単位（３）の含有量は、全繰返し単位の合計量に対して、好ましくは１０～３５モル％、より好ましくは１５～３０モル％、さらに好ましくは１７．５～２７．５モル％である。このような所定の繰返し単位組成を有する液晶ポリエステルは、耐熱性と成形性とのバランスに優れている。なお、繰返し単位（２）の含有量と繰返し単位（３）の含有量とは、実質的に等しいことが好ましい。また、液晶ポリエステルは、必要に応じて繰返し単位（１）～（３）以外の繰返し単位を有していてもよいが、その含有量は、全繰返し単位の合計量に対して、通常１０モル％以下、好ましくは５モル％以下である。 In the liquid crystal polyester, 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. In addition, it is preferable that content of a repeating unit (2) and content of a repeating unit (3) are substantially equal. 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.
　耐熱性や溶融張力が高い液晶ポリエステルの典型的な例は、全繰返し単位の合計量に対して、Ａｒ1が２，６－ナフチレン基である繰返し単位（１）、すなわち６－ヒドロキシ－２－ナフトエ酸に由来する繰返し単位を、好ましくは４０～７４．８モル％、より好ましくは４０～６４．５モル％、さらに好ましくは５０～５８モル％有し、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）、すなわち２，６－ナフタレンジカルボン酸に由来する繰返し単位を、好ましくは１２．５～３０モル％、より好ましくは１７．５～３０モル％、さらに好ましくは２０～２５モル％有し、Ａｒ2が１，４－フェニレン基である繰返し単位（２）、すなわちテレフタル酸に由来する繰返し単位を、好ましくは０．２～１５モル％、より好ましくは０．５～１２モル％、さらに好ましくは２～１０モル％有し、Ａｒ3が１，４－フェニレン基である繰返し単位（３）、すなわちヒドロキノンに由来する繰返し単位を、好ましくは１２．５～３０モル％、より好ましくは１７．５～３０モル％、さらに好ましくは２０～２５モル％有し、かつ、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）の含有量が、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）及びＡｒ2が１，４－フェニレン基である繰返し単位（２）の合計含有量に対して、好ましくは０．５モル倍以上、より好ましくは０．６モル倍以上のものである。 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%. a mole%, 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.
　液晶ポリエステルは、繰返し単位（１）を与えるモノマー、すなわち所定の芳香族ヒドロキシカルボン酸と、繰返し単位（２）を与えるモノマー、すなわち所定の芳香族ジカルボン酸と、繰返し単位（３）を与えるモノマー、すなわち所定の芳香族ジオールとを、２，６－ナフチレン基を有するモノマーの合計量、すなわち６－ヒドロキシ－２－ナフトエ酸、２，６－ナフタレンジカルボン酸及び２，６－ナフタレンジオールの合計量が、全モノマーの合計量に対して、４０モル％以上になるようにして、重合（重縮合）させることにより、製造することができる。その際、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸及び芳香族ジオールのそれぞれの一部又は全部に代えて、その重合可能な誘導体を用いてもよい。芳香族ヒドロキシカルボン酸及び芳香族ジカルボン酸のようなカルボキシル基を有する化合物の重合可能な誘導体の例としては、カルボキシル基をアルコキシカルボニル基やアリールオキシカルボニル基に変換してなるもの、カルボキシル基をハロホルミル基に変換してなるもの、カルボキシル基をアシルオキシカルボニル基に変換してなるものが挙げられる。芳香族ヒドロキシカルボン酸及び芳香族ジオールのようなヒドロキシル基を有する化合物の重合可能な誘導体の例としては、ヒドロキシル基をアシル化してアシルオキシル基に変換してなるものが挙げられる。 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. At that time, instead of some or all of the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid and aromatic diol, polymerizable derivatives thereof may be used. Examples of polymerizable derivatives of compounds having a carboxyl group such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group, and a carboxyl group as a haloformyl. And a group formed by converting a carboxyl group into an acyloxycarbonyl group. Examples of 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.
　また、液晶ポリエステルは、モノマーを溶融重合させ、得られた重合物（プレポリマー）を固相重合させることにより、製造することが好ましい。これにより、耐熱性や溶融張力が高い液晶ポリエステルを操作性良く製造することができる。溶融重合は、触媒の存在下に行ってもよく、この触媒の例としては、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモン等の金属化合物や、Ｎ，Ｎ－ジメチルアミノピリジン、Ｎ－メチルイミダゾール等の含窒素複素環式化合物が挙げられ、含窒素複素環式化合物が好ましく用いられる。 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. Examples of 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.
　液晶ポリエステルは、その流動開始温度が、好ましくは２８０℃以上、より好ましくは２９０℃以上、さらに好ましくは２９５℃以上であり、また、通常３８０℃以下、好ましくは３５０℃以下である。流動開始温度が高いほど、耐熱性や溶融張力が向上し易いが、あまり高いと、溶融させるために高温を要し、成形時に熱劣化し易くなる。 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. As 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.
　なお、流動開始温度は、フロー温度又は流動温度とも呼ばれ、内径１ｍｍ、長さ１０ｍｍのノズルを持つ毛細管レオメータを用い、９．８ＭＰａ（１００ｋｇ／ｃｍ2）の荷重下において、４℃／分の昇温速度で液晶ポリエステルの加熱溶融体をノズルから押し出すときに、溶融粘度が４８００Ｐａ・ｓ（４８，０００ポイズ）を示す温度であり、液晶ポリエステルの分子量の目安となるものである（小出直之編、「液晶ポリマー－合成・成形・応用－」、株式会社シーエムシー、１９８７年６月５日、ｐ．９５参照）。 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 rate of temperature rise, and is a measure of the molecular weight of the liquid crystal polyester (Naoyuki Koide) Ed., “Liquid Crystal Polymers—Synthesis / Molding / Application—”, CMC Corporation, June 5, 1987, p. 95).
　こうして得られる液晶ポリエステルは、水蒸気バリア性に優れており、厚さ５０μｍのフィルムにしたときの温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が、通常０．１ｇ／ｍ2・２４ｈ以下、好ましくは０．０５ｇ／ｍ2・２４ｈ以下、より好ましくは０．０１ｇ／ｍ2・２４ｈ以下、さらに好ましくは０．００５ｇ／ｍ2・２４ｈ以下となる。 The liquid crystal polyester 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% when formed into a film having a thickness of 50 μm is usually 0.1 g / m 2. 24h or less, preferably 0.05 g / m 2 · 24h or less, more preferably 0.01 g / m 2 · 24h or less, more preferably less than or equal to 0.005g / m 2 · 24h.
　液晶ポリエステルには、必要に応じて他の成分を配合して、組成物としてもよい。他の成分の例としては、充填材、液晶ポリエステル以外の熱可塑性樹脂及び添加剤が挙げられる。組成物全体に占める液晶ポリエステルの割合は、好ましくは８０質量％以上であり、より好ましくは９０質量％以上である。 The liquid crystal polyester may be blended with other components as necessary to form a composition. Examples of 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.
　充填材の例としては、ミルドガラスファイバー、チョップドガラスファイバー等のガラス繊維、チタン酸カリウムウイスカー、アルミナウイスカ、ホウ酸アルミニウムウイスカ、炭化けい素ウイスカ、窒化けい素ウイスカ等の金属又は非金属系ウイスカ類、ガラスビーズ、中空ガラス球、ガラス粉末、マイカ、タルク、クレー、シリカ、アルミナ、チタン酸カリウム、ウォラスナイト、炭酸カルシウム（重質、軽質、膠質等）、炭酸マグネシウム、塩基性炭酸マグネシウム、硫酸ソーダ、硫酸カルシウム、硫酸バリウム、亜硫酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、けい酸カルシウム、けい砂、けい石、石英、酸化チタン、酸化亜鉛、酸化鉄グラファイト、モリブデン、アスベスト、シリカアルミナ繊維、アルミナ繊維、石膏繊維、炭素繊維、カーボンブラック、ホワイトカーボン、けいそう土、ベントナイト、セリサイト、シラス及び黒鉛が挙げられ、必要に応じてそれらの２種以上を用いることもできる。中でも、ガラス繊維、マイカ、タルク及び炭素繊維が好ましく用いられる。 Examples of 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 beads, hollow glass spheres, glass powder, mica, talc, clay, silica, alumina, potassium titanate, wollastonite, calcium carbonate (heavy, light, colloidal, etc.), magnesium carbonate, basic magnesium carbonate, sodium sulfate , Calcium sulfate, barium sulfate, calcium sulfite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium silicate, silica sand, silica, quartz, titanium oxide, zinc oxide, iron oxide graphite, molybdenum, asbestos, silica alumina Wei, alumina fibers, gypsum fibers, carbon fibers, carbon black, white carbon, diatomaceous earth, bentonite, sericite, Shirasu and graphite are mentioned, it is also possible to use two or more of them, if necessary. Among these, glass fiber, mica, talc and carbon fiber are preferably used.
　充填材は、必要に応じて、表面処理されたものであってもよく、この表面処理剤の例としては、シラン系カップリング剤、チタネート系カップリング剤、ボラン系カップリング剤等の反応性カップリング剤、及び高級脂肪酸、高級脂肪酸エステル、高級脂肪酸金属塩、フルオロカーボン系界面活性剤等の潤滑剤が挙げられる。 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 include coupling agents and lubricants such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants.
　充填材の配合量は、液晶ポリエステル１００質量部に対して、通常０．１～２０質量部、好ましくは０．５～１５質量部、より好ましくは０．５～１０質量部である。 The blending amount of the filler is usually 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester.
　液晶ポリエステル以外の熱可塑性樹脂の例としては、ポリカーボネート、ポリアミド、ポリサルフォン、ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリエーテルケトン及びポリエーテルイミド樹脂が挙げられる。 Examples of thermoplastic resins other than liquid crystal polyester include polycarbonate, polyamide, polysulfone, polyphenylene sulfide, polyphenylene ether, polyether ketone, and polyetherimide resin.
　添加剤の例としては、フッ素樹脂、金属石鹸類等の離型改良剤、核剤、酸化防止剤、安定剤、可塑剤、滑剤、着色防止剤、着色剤、紫外線吸収剤、帯電防止剤、潤滑剤及び難燃剤が挙げられる。 Examples of 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.
　こうして得られる液晶ポリエステル又はその組成物をフィルム化することにより、本発明の有機ＥＬ用基板の液晶ポリエステル層２３となる液晶ポリエステルフィルムを得ることができる。フィルム化の方法としては、例えば、押出成形法、プレス成形法、溶液流延法及び射出成形法が挙げられ、押出成形法が好ましい。押出成形法としては、例えば、Ｔダイ法やインフレーション法が挙げられ、Ｔダイ法において、一軸延伸してもよいし、二軸延伸してもよい。 A liquid crystal polyester film to be the liquid crystal polyester layer 23 of the organic EL substrate of the present invention can be obtained by forming the liquid crystal polyester thus obtained or a composition thereof into a film. Examples of 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. Examples of 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.
　一軸延伸フィルムの延伸倍率（ドラフト比）は、通常１．１～４０、好ましくは１０～４０、より好ましくは１５～３５である。二軸フィルムのＭＤ方向（押出方向）の延伸倍率は、通常１．２～４０倍であり、二軸フィルムのＴＤ方向（押出方向に垂直な方向）の延伸倍率は、通常１．２～２０倍である。インフレーションフィルムのＭＤ方向の延伸倍率（ドローダウン比＝バブル引取速度／樹脂吐出速度）は、通常１．５～５０、好ましくは５～３０であり、インフレーションフィルムのＴＤの延伸倍率（ブロー比＝バブル径／環状スリット径）は、通常１．５～１０、好ましくは２～５である。 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 stretch ratio in the MD direction of the inflation film (drawdown ratio = bubble take-off speed / resin discharge speed) is usually 1.5 to 50, preferably 5 to 30, and the stretch ratio of TD of the inflation film (blow ratio = bubble) Diameter / annular slit diameter) is usually 1.5 to 10, preferably 2 to 5.
　液晶ポリエステル層２３の厚さは、好ましくは５～５００μｍであり、より好ましくは１０～２５０μｍであり、さらに好ましくは１５～２００μｍである。あまり薄いと、強度が不十分になり、あまり厚いと、フレキシブル性が不十分になる。 The thickness of the liquid crystal polyester layer 23 is preferably 5 to 500 μm, more preferably 10 to 250 μm, and further preferably 15 to 200 μm. If it is too thin, the strength will be insufficient, and if it is too thick, the flexibility will be insufficient.
　液晶ポリエステル層２３は、水蒸気バリア性に優れており、温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が、通常０．１ｇ／ｍ2・２４ｈ以下、好ましくは０．０５ｇ／ｍ2・２４ｈ以下、より好ましくは０．０１ｇ／ｍ2・２４ｈ以下、さらに好ましくは０．００５ｇ／ｍ2・２４ｈ以下となる。 The liquid crystal polyester layer 23 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 usually 0.1 g / m 2 · 24 h or less, preferably 0.05 g / m. 2 · 24h or less, more preferably 0.01g / m 2 · 24h or less, more preferably less than or equal to 0.005g / m 2 · 24h.
　液晶ポリエステル層２３には、その少なくとも一方の面上に、水蒸気バリア層２４が設けられてもよい。すなわち、液晶ポリエステル層２３となる液晶ポリエステルフィルムは、その少なくとも一方の面上に、水蒸気バリア層２４を設けて、積層フィルムとしてもよい。なお、図２の例では、液晶ポリエステル層２３の裏側に、水蒸気バリア層２４が設けられているが、液晶ポリエステル層２３の表側に設けられてもよいし、液晶ポリエステル層２３の表側と裏側とに設けられてもよい。 The liquid crystal polyester layer 23 may be provided with a water vapor barrier layer 24 on at least one surface thereof. That is, the liquid crystal polyester film to be the liquid crystal polyester layer 23 may be a laminated film by providing the water vapor barrier layer 24 on at least one surface thereof. In the example of FIG. 2, the water vapor barrier layer 24 is provided on the back side of the liquid crystal polyester layer 23, but may be provided on the front side of the liquid crystal polyester layer 23, and the front side and back side of the liquid crystal polyester layer 23 May be provided.
　水蒸気バリア層２４を構成する物質としては、アルミニウム、ケイ素、チタン、クロム、鉄、コバルト、ニッケル、銅、亜鉛、銀及び金からなる群から選ばれる少なくとも１種の元素の単体、酸化物、窒化物及び酸窒化物が好ましく、必要に応じてそれらの２種以上を用いてもよい。 Substances constituting the water vapor barrier layer 24 include at least one element selected from the group consisting of aluminum, silicon, titanium, chromium, iron, cobalt, nickel, copper, zinc, silver and gold, oxide, and nitridation. And oxynitrides are preferable, and two or more of them may be used as necessary.
水蒸気バリア層２４の形成方法としては、例えば、蒸着法、スパッタリング法、イオンプレーティング法等のＰＶＤ法、プラズマＣＶＤ法、熱ＣＶＤ法、レーザーＣＶＤ法等のＣＶＤ法、及びゾル－ゲル法、めっき法、塗布法等のウェット法が挙げられる。また、別途調製乃至入手した箔を、液晶ポリエステルフィルムに貼合してもよい。 Examples of the method for forming the water vapor barrier layer 24 include PVD methods such as vapor deposition, sputtering, and ion plating, CVD methods such as plasma CVD, thermal CVD, and laser CVD, sol-gel methods, and plating. And wet methods such as coating method and coating method. Further, a foil prepared or obtained separately may be bonded to the liquid crystal polyester film.
　水蒸気バリア層２４の厚さは、好ましくは５～２５０ｎｍ、より好ましくは４０～１００ｎｍである。あまり薄いと、水蒸気バリア性が不十分になり、あまり厚いと、フレキシブル性が不十分になる。 The thickness of the water vapor barrier layer 24 is preferably 5 to 250 nm, more preferably 40 to 100 nm. If it is too thin, the water vapor barrier property will be insufficient, and if it is too thick, the flexibility will be insufficient.
　こうして構成される液晶ポリエステル層２３と水蒸気バリア層２４との積層体は、水蒸気バリア性に優れており、温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が、通常０．００５ｇ／ｍ2・２４ｈ以下、好ましくは０．００１ｇ／ｍ2・２４ｈ以下、より好ましくは０．０００５ｇ／ｍ2・２４ｈ以下、さらに好ましくは０．０００１ｇ／ｍ2・２４ｈ以下となる。 The laminate of the liquid crystal polyester layer 23 and the water vapor barrier layer 24 thus configured 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 usually 0.005 g / m 2 · 24h or less, preferably 0.001g / m 2 · 24h or less, more preferably 0.0005g / m 2 · 24h or less, more preferably less than or equal to 0.0001g / m 2 · 24h.
　液晶ポリエステル層２３の裏側には、白色顔料含有層２６が設けられる。これにより、耐候性に優れる有機ＥＬ用基板２を得ることができる。なお、図２の例では、接着層２５を介して、白色顔料含有層２６が設けられているが、接着層２５を介さずに、例えば熱融着により白色顔料含有層２６が設けられてもよい。 A white pigment-containing layer 26 is provided on the back side of the liquid crystal polyester layer 23. Thereby, the organic EL substrate 2 excellent in weather resistance can be obtained. In the example of FIG. 2, the white pigment-containing layer 26 is provided via the adhesive layer 25, but the white pigment-containing layer 26 may be provided by thermal fusion, for example, without using the adhesive layer 25. Good.
　白色顔料含有層２６に含まれる白色顔料としては、塩基性炭酸鉛（２ＰｂＣＯ3・Ｐｂ（ＯＨ）2（鉛白）等）、塩基性硫酸鉛（２ＰｂＳＯ4・Ｐｂ（ＯＨ）2等）、塩基性ケイ酸鉛（Ｐｂ2ＳｉＯ4・Ｐｂ（ＯＨ）2等）、亜鉛華（ＺｎＯ（酸化亜鉛））、硫化亜鉛、リトポン（硫化亜鉛と硫酸バリウムとの混合物）、三酸化アンチモン及び酸化チタンが好ましく、必要に応じてそれらの２種以上を用いてもよい。 White pigments contained in the white pigment-containing layer 26 include basic lead carbonate (2PbCO 3 · Pb (OH) 2 (lead white), etc.), basic lead sulfate (2PbSO 4 · Pb (OH) 2 etc.), base Lead silicate (Pb 2 SiO 4 · Pb (OH) 2 etc.), zinc white (ZnO (zinc oxide)), zinc sulfide, lithopone (mixture of zinc sulfide and barium sulfate), antimony trioxide and titanium oxide Preferably, two or more of them may be used as necessary.
　白色顔料含有層２６は、白色顔料を含む樹脂フィルムを用いて設けることが好ましく、この樹脂フィルムすなわち白色顔料含有層２６に含まれる樹脂としては、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステルが好ましい。白色顔料含有層中の白色顔料の含有量は、白色顔料含有層の全量に対して、好ましくは５～９０質量％、より好ましくは１０～８０質量％である。また、白色顔料含有層５６の厚さは、好ましくは５～５００μｍ、より好ましくは１０～４００μｍである。 The white pigment-containing layer 26 is preferably provided using a resin film containing a white pigment, and the resin film, that is, the resin contained in the white pigment-containing layer 26 is preferably a polyester such as polyethylene terephthalate (PET). The content of the white pigment in the white pigment-containing layer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on the total amount of the white pigment-containing layer. The thickness of the white pigment-containing layer 56 is preferably 5 to 500 μm, more preferably 10 to 400 μm.
　液晶ポリエステル層２３表側には、意匠性を付与するために、他の樹脂層、好ましくはポリオレフィン層２１を設けてもよい。なお、図２の例では、接着層２２を介して、ポリオレフィン層２１が設けられているが、接着層２２を介さずに、例えば熱融着によりポリオレフィン層２１が設けられてもよい。 The liquid crystal polyester layer 23 may be provided on the front side with another resin layer, preferably a polyolefin layer 21, in order to impart design properties. In the example of FIG. 2, the polyolefin layer 21 is provided via the adhesive layer 22, but the polyolefin layer 21 may be provided by, for example, thermal fusion without using the adhesive layer 22.
　ポリオレフィン層２１を構成するポリオレフィンは、好ましくはポリエチレン、より好ましくは低密度ポリエチレン（ＬＤＰＥ）、さらに好ましくは直鎖状低密度ポリエチレン（ＬＬＤＰＥ）である。ポリオレフィン層２１は、ポリオレフィンフィルムを用いて設けることが好ましく、意匠性を付与するためにポリオレフィン層２１を設ける場合は、ポリオレフィンフィルムすなわちポリオレフィン層２１に、所望の色の顔料や染料を含ませればよい。ポリオレフィン層２１の厚さは、好ましくは５～２００μｍ、より好ましくは１０～１００μｍである。 The polyolefin constituting the polyolefin layer 21 is preferably polyethylene, more preferably low density polyethylene (LDPE), and still more preferably linear low density polyethylene (LLDPE). The polyolefin layer 21 is preferably provided using a polyolefin film. When the polyolefin layer 21 is provided in order to impart designability, a desired color pigment or dye may be included in the polyolefin film, that is, the polyolefin layer 21. . The thickness of the polyolefin layer 21 is preferably 5 to 200 μm, more preferably 10 to 100 μm.
　こうして得られる本発明の有機ＥＬ用基板は、図１に示す如く、その上に、一対の電極４Ａ，４Ｂが配置され、この一対の電極４Ａ，４Ｂの間に、有機ＥＬ層５が配置される。図２に示すように、有機ＥＬ用基板２が、液晶ポリエステル層２３の一方の面上のみに水蒸気バリア層２４を有する場合、液晶ポリエステル層２３の水蒸気バリア層２４が配置された面とは反対側の面上に、一対の電極４Ａ，４Ｂ及び有機ＥＬ層５を配置することが好ましい。 As shown in FIG. 1, the organic EL substrate of the present invention thus obtained has a pair of electrodes 4A and 4B disposed thereon, and the organic EL layer 5 is disposed between the pair of electrodes 4A and 4B. The As shown in FIG. 2, when the organic EL substrate 2 has the water vapor barrier layer 24 only on one surface of the liquid crystal polyester layer 23, it is opposite to the surface of the liquid crystal polyester layer 23 on which the water vapor barrier layer 24 is disposed. It is preferable to arrange a pair of electrodes 4A and 4B and an organic EL layer 5 on the side surface.
　なお、図１では、有機ＥＬ用基板２の上に、陰極４Ａ、有機ＥＬ層５及び陽極４Ｂがこの順に配置されているが、有機ＥＬ用基板２の上に、陽極４Ｂ、有機ＥＬ層５及び陰極４Ａがこの順に配置されていてもよい。また、図１では、有機ＥＬ層５が、発光層５ｂと、その陰極４Ａ側に配置された電子輸送層５ａと、その陽極４Ｂ側に配置された正孔輸送層５ｃとから構成されているが、発光層５ｂ及び電子輸送層５ａに代えて、両者の機能を備える発光層兼電子輸送層を有してもよいし、発行層５ｂ及び正孔輸送層５ｃに代えて、両者の機能を備える発光層兼正孔輸送層を有してもよい。 In FIG. 1, the cathode 4A, the organic EL layer 5 and the anode 4B are arranged in this order on the organic EL substrate 2, but the anode 4B and the organic EL layer 5 are arranged on the organic EL substrate 2. And the cathode 4A may be arranged in this order. Moreover, in FIG. 1, the organic EL layer 5 is comprised from the light emitting layer 5b, the electron carrying layer 5a arrange | positioned at the cathode 4A side, and the positive hole transport layer 5c arrange | positioned at the anode 4B side. However, in place of the light emitting layer 5b and the electron transport layer 5a, a light emitting layer / electron transport layer having both functions may be provided, or in place of the issue layer 5b and the hole transport layer 5c, both functions may be provided. You may have a light emitting layer and hole transport layer provided.
　発光層５ｂの材料は、高分子型であってもよいし、低分子型であってもよい。また、陰極４Ａ及び陽極４Ｂの材料は、それぞれ独立に、アルミニウム、銅等の金属であってもよいし、インジム錫オキシド、亜鉛錫オキシド等の金属酸化物であってもよいが、発光層５ｂから発せられる光を透すために、少なくとも一方に透明性が求められる。本発明の有機ＥＬ用基板２は、液晶ポリエステル層を有し、通常、透明性に劣るため、これを基板とする有機ＥＬ素子１は、発光層５ｂから有機ＥＬ用基板２とは反対側の方向に光が発せられるトップエミッションタイプであることが好ましい。そして、有機ＥＬ素子１がトップエミッションタイプの場合、発光層５ｂを基準に、有機ＥＬ用基板２とは反対側に配置される電極（図１では陽極４Ｂ）に透明性が求められ、その上に配置される封止層６にも、透明性が求められる。 The material of the light emitting layer 5b may be a polymer type or a low molecular type. The materials of the cathode 4A and the anode 4B may be independently metals such as aluminum and copper, or may be metal oxides such as indium tin oxide and zinc tin oxide, but the light emitting layer 5b. In order to transmit the light emitted from, at least one of them is required to be transparent. Since the organic EL substrate 2 of the present invention has a liquid crystal polyester layer and is usually inferior in transparency, the organic EL element 1 using this layer as a substrate is opposite to the organic EL substrate 2 from the light emitting layer 5b. It is preferable that the top emission type emit light in the direction. And when the organic EL element 1 is a top emission type, transparency is calculated | required by the electrode (anode 4B in FIG. 1) arrange | positioned on the opposite side to the board | substrate 2 for organic EL on the basis of the light emitting layer 5b. The sealing layer 6 disposed on the substrate is also required to have transparency.
　封止層６としては、水蒸気バリア性の点では、ガラス板が好ましいが、フレキシブル性の点では、樹脂フィルムが好ましい。封止材３としては、紫外線硬化型樹脂が好ましく用いられる。また、封止層６として、ガラス板や樹脂フィルムの如き板状部材を用いずに、紫外線硬化型樹脂の如き封止材で、一対の電極及び有機ＥＬ層を覆ってもよい。 The sealing layer 6 is preferably a glass plate in terms of water vapor barrier properties, but is preferably a resin film in terms of flexibility. As the sealing material 3, an ultraviolet curable resin is preferably used. Further, as the sealing layer 6, a pair of electrodes and the organic EL layer may be covered with a sealing material such as an ultraviolet curable resin without using a plate-like member such as a glass plate or a resin film.
　こうして得られる有機ＥＬ素子は、基板として、耐候性に優れる本発明の有機ＥＬ用基板を用いているので、例えば、反射光により裏側から長期間にわたり光照射を受けても、反り難く、剥がれたり、破れたりし難い。 Since the organic EL device thus obtained uses the organic EL substrate of the present invention having excellent weather resistance as the substrate, for example, even if it is irradiated with light from the back side for a long time by reflected light, it is difficult to warp and peel off. It ’s hard to break.
〔流動開始温度の測定〕
　フローテスター（（株）島津製作所製の「ＣＦＴ－５００型」）を用いて、試料約２ｇを、内径１ｍｍ、長さ１０ｍｍのダイスを取り付けた毛細管型レオメーターに充填し、９．８ＭＰａ（１００ｋｇｆ／ｃｍ2）の荷重下において、昇温速度４℃／分で試料を溶融させながら押し出し、溶融粘度が４８００Ｐａ・ｓ（４８０００ポイズ）を示す温度を測定した。 [Measurement of flow start temperature]
Using a flow tester (“CFT-500 type” manufactured by Shimadzu Corporation), about 2 g of the sample was filled into a capillary rheometer equipped with a die having an inner diameter of 1 mm and a length of 10 mm, and 9.8 MPa (100 kgf / Cm 2 ), the sample was extruded while melting at a heating rate of 4 ° C./min, and the temperature at which the melt viscosity was 4800 Pa · s (48000 poise) was measured.
〔水蒸気バリア性の評価〕
　ＪＩＳ　Ｋ７１２９　Ｃ法に準拠して、ガス透過率・透湿度測定装置（ＧＴＲテック（株）の「ＧＴＲ－３０Ｘ」）により、温度４０℃、相対湿度９０％の条件で、水蒸気透過度を測定した。 [Evaluation of water vapor barrier properties]
In accordance with JIS K7129 C method, the water vapor transmission rate was measured at a temperature of 40 ° C. and a relative humidity of 90% with a gas permeability / moisture permeability measuring device (“GTR-30X” from GTR Tech Co., Ltd.). .
〔耐候性の評価〕
　促進耐光性試験機（スガ試験機（株）の「強エネルギーキセノンウェザーメーターＳＣ７００－ＷＮ」）を用いて、バックシートに次の条件でキセノン照射を行い、バックシートの外観を目視で観察した。
波長：２７５ｎｍ以上の連続光（フィルターにより短波長側をカット）
強度：１６０Ｗ／ｍ2（ランプ出力）
温度：６５℃（照射面と同位置のフラットパネル温度計により測定）
時間：６０時間 [Evaluation of weather resistance]
Using an accelerated light resistance tester (“Strong Energy Xenon Weather Meter SC700-WN” from Suga Test Instruments Co., Ltd.), the backsheet was irradiated with xenon under the following conditions, and the appearance of the backsheet was visually observed.
Wavelength: Continuous light of 275nm or more (short wavelength side is cut by a filter)
Intensity: 160 W / m 2 (Lamp output)
Temperature: 65 ° C (measured with a flat panel thermometer at the same position as the irradiated surface)
Time: 60 hours
製造例１（１）
　攪拌装置、トルクメータ、窒素ガス導入管、温度計および還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１０３４．９９ｇ（５．５モル）、２，６－ナフタレンジカルボン酸３７８．３３ｇ（１．７５モル）、テレフタル酸８３．０７ｇ（０．５モル）、ヒドロキノン２７２．５２ｇ（２．４７５モル：２，６－ナフタレンジカルボン酸及びテレフタル酸の合計量に対して０．２２５モル過剰）、無水酢酸１２２６．８７ｇ（１２モル）、及び触媒として１－メチルイミダゾール０．１７ｇを入れ、反応器内のガスを窒素ガスで置換した後、窒素ガス気流下、攪拌しながら、室温から１４５℃まで１５分かけて昇温し、１４５℃で１時間還流させた。次いで、副生酢酸及び未反応の無水酢酸を留去しながら、１４５℃から３１０℃まで３時間３０分かけて昇温し、３１０℃で３時間保持した後、内容物を取り出し、室温まで冷却した。得られた固形物を、粉砕機で粒径約０．１～１ｍｍに粉砕後、窒素雰囲気下、室温から２５０℃まで１時間かけて昇温し、２５０℃から３１０℃まで１０時間かけて昇温し、３１０℃で５時間保持することにより、固相重合を行った。固相重合後、冷却して、粉末状の液晶ポリエステルを得た。この液晶ポリエステルは、全繰り返し単位の合計量に対して、Ａｒ1が２，６－ナフチレン基である繰返し単位（１）を５５モル％、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）を１７．５モル％、Ａｒ2が１，４－フェニレン基である繰返し単位（２）を５モル％、及びＡｒ3が１，４－フェニレン基である繰返し単位（３）を２２．５％有し、その流動開始温度は３３３℃であった。 Production Example 1 (1)
To a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 103.499 g (5.5 mol) of 6-hydroxy-2-naphthoic acid, 378 of 2,6-naphthalenedicarboxylic acid 378 0.33 g (1.75 mol), 83.07 g (0.5 mol) of terephthalic acid, 272.52 g of hydroquinone (2.475 mol: 0.225 based on the total amount of 2,6-naphthalenedicarboxylic acid and terephthalic acid) Molar excess), 1226.87 g (12 moles) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst, and after replacing the gas in the reactor with nitrogen gas, stirring at room temperature under a nitrogen gas stream To 145 ° C. over 15 minutes and refluxed at 145 ° C. for 1 hour. Next, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 145 ° C. to 310 ° C. over 3 hours and 30 minutes, held at 310 ° C. for 3 hours, then the contents were taken out and cooled to room temperature did. The obtained solid is pulverized to a particle size of about 0.1 to 1 mm with a pulverizer, then heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, and then increased from 250 ° C. to 310 ° C. over 10 hours. Solid state polymerization was performed by warming and holding at 310 ° C. for 5 hours. After solid state polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester. In this liquid crystalline polyester, 55 mol% of the repeating unit (1) in which Ar 1 is a 2,6-naphthylene group and Ar 2 is a 2,6-naphthylene group in terms of the total amount of all repeating units ( 2) 17.5 mol%, Ar 2 is 1,4-phenylene group repeating unit (2) 5 mol%, and Ar 3 is 1,4-phenylene group repeating unit (3) 22. 5%, and the flow start temperature was 333 ° C.
製造例２（１）
　製造例１と同様の反応器に、ｐ－ヒドロキシ安息香酸９１１ｇ（６．６モル）、イソフタル酸９１ｇ（０．５５モル）、テレフタル酸２７４ｇ（１．６５モル）、４，４’－ジヒドロキシビフェニル４０９ｇ（２．２モル）、無水酢酸１２３５ｇ（１２．１モル）、及び触媒として１－メチルイミダゾール０．１７ｇを入れ、反応器内のガスを窒素ガスで置換した後、窒素ガス気流下、攪拌しながら、室温から１５０℃まで１５分かけて昇温し、１５０℃で１時間還流させた。次いで、１－メチルイミダゾール１．７ｇを添加した後、副生酢酸及び未反応の無水酢酸を留去しながら、１５０℃から３２０℃まで２時間５０分かけて昇温し、トルクの上昇が認められた時点で、内容物を取り出し、室温まで冷却した。得られた固形物を、粉砕機で粒径約０．１～１ｍｍに粉砕後、窒素雰囲気下、室温から２５０℃まで１時間かけて昇温し、２５０℃から２８５℃まで５時間かけて昇温し、２８５℃で３時間保持することにより、固相重合を行った。固相重合後、冷却して、粉末状の液晶ポリエステルを得た。この液晶ポリエステルの流動開始温度は、３２７℃であった。 Production Example 2 (1)
In the same reactor as in Production Example 1, 911 g (6.6 mol) of p-hydroxybenzoic acid, 91 g (0.55 mol) of isophthalic acid, 274 g (1.65 mol) of terephthalic 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. Next, after adding 1.7 g of 1-methylimidazole, the temperature was raised from 150 ° C. to 320 ° C. over 2 hours and 50 minutes while distilling off by-product acetic acid and unreacted acetic anhydride, and an increase in torque was observed. At that time, the contents were removed and cooled to room temperature. The obtained solid is pulverized to a particle size of about 0.1 to 1 mm with a pulverizer, then heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, and then increased from 250 ° C. to 285 ° C. over 5 hours. Solid state polymerization was performed by warming and holding at 285 ° C. for 3 hours. After solid state polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester. The liquid crystal polyester had a flow initiation temperature of 327 ° C.
製造例１（２）
　製造例１（１）で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ５０μｍの液晶ポリエステルを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．００３０ｇ／ｍ2・２４ｈであった。 Production Example 1 (2)
The liquid crystalline polyester obtained in Production Example 1 (1) was granulated with a twin-screw extruder (“PCM-30” from Ikegai Co., Ltd.), pelletized, and then put into a single-screw extruder (screw diameter 50 mm). It was supplied and melted, 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 having a thickness of 50 μm. The water vapor permeability of this liquid crystal polyester film was 0.0030 g / m 2 · 24 h.
製造例２（２）
　製造例２（１）で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ５０μｍの液晶ポリエステルを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．０８０ｇ／ｍ2・２４ｈであった。 Production Example 2 (2)
The liquid crystalline polyester obtained in Production Example 2 (1) was granulated with a twin screw extruder ("PCM-30" by Ikegai Co., Ltd.), pelletized, and then put into a single screw extruder (screw diameter 50 mm). It was supplied and melted, 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 having a thickness of 50 μm. The water vapor permeability of this liquid crystal polyester film was 0.080 g / m 2 · 24 h.
製造例１（３）
　製造例１（２）で得られた液晶ポリエステルフィルムの片面に、ガスバリア層として厚さ２０ｎｍのアルミニウム酸化物薄膜を形成し、積層フィルムを得た。この積層フィルムの水蒸気透過度は、０．０００１ｇ／ｍ2・２４ｈ未満（検出下限値未満）であった。 Production Example 1 (3)
An aluminum oxide thin film having a thickness of 20 nm was formed as a gas barrier layer on one side of the liquid crystal polyester film obtained in Production Example 1 (2) to obtain a laminated film. The water vapor permeability of this laminated film was less than 0.0001 g / m 2 · 24 h (less than the detection lower limit).
製造例２（３）
　製造例２（２）で得られた液晶ポリエステルフィルムの片面に、ガスバリア層として厚さ２０ｎｍのアルミニウム酸化物薄膜を形成し、積層フィルムを得た。この積層フィルムの水蒸気透過度は、０．００２０ｇ／ｍ2・２４ｈであった。 Production Example 2 (3)
An aluminum oxide thin film having a thickness of 20 nm was formed as a gas barrier layer on one side of the liquid crystal polyester film obtained in Production Example 2 (2) to obtain a laminated film. The water vapor permeability of this laminated film was 0.0020 g / m 2 · 24 h.
実施例１
　厚さ２５０μｍの白色ＰＥＴフィルム（東レ（株）の「ルミラーＥ２０」：酸化チタン含有）の片面に、ウレタン系接着剤（三井武田ケミカル（株）：主剤「タケラックＡ５１１」／硬化剤「Ａ５０」＝１０／１（質量比））を塗布し、製造例１（２）で得られた液晶ポリエステルフィルムを貼り合わせ、積層フィルムを得た。次いで、この積層フィルムの液晶ポリエステルフィルム面に、ウレタン系接着剤（同上）を塗布し、厚さ５０μｍのＬＬＤＰＥフィルムを貼り合わせ、積層フィルムを得た。得られたバックシートについて、白色ＰＥＴフィルム側からキセノン照射することにより、耐候性を評価した結果、反り等の形状変化や破れは見られなかった。 Example 1
A urethane adhesive (Mitsui Takeda Chemical Co., Ltd .: main agent “Takelac A511” / curing agent “A50”) on one side of a 250 μm thick white PET film (Tolu Co., Ltd. “Lumirror E20”: containing titanium oxide) = 10/1 (mass ratio)) was applied, and the liquid crystal polyester film obtained in Production Example 1 (2) was bonded to obtain a laminated film. Next, a urethane adhesive (same as above) was applied to the liquid crystal polyester film surface of the laminated film, and an LLDPE film having a thickness of 50 μm was bonded to obtain a laminated film. As a result of evaluating the weather resistance of the obtained back sheet by irradiating xenon from the white PET film side, no shape change such as warping or tearing was observed.
実施例２
　厚さ２５０μｍの白色ＰＥＴフィルム（東レ（株）の「ルミラーＥ２０」：酸化チタン含有）の片面に、ウレタン系接着剤（三井武田ケミカル（株）：主剤「タケラックＡ５１１」／硬化剤「Ａ５０」＝１０／１（質量比））を塗布し、製造例２（２）で得られた液晶ポリエステルフィルムを貼り合わせ、積層フィルムを得た。次いで、この積層フィルムの液晶ポリエステルフィルム面に、ウレタン系接着剤（同上）を塗布し、厚さ５０μｍのＬＬＤＰＥフィルムを貼り合わせ、バックシートを得た。得られた積層フィルムについて、白色ＰＥＴフィルム側からキセノン照射することにより、耐候性を評価した結果、反り等の形状変化や破れは見られなかった。 Example 2
A urethane adhesive (Mitsui Takeda Chemical Co., Ltd .: main agent “Takelac A511” / curing agent “A50”) on one side of a 250 μm thick white PET film (Tolu Co., Ltd. “Lumirror E20”: containing titanium oxide) = 10/1 (mass ratio)) was applied, and the liquid crystal polyester film obtained in Production Example 2 (2) was bonded to obtain a laminated film. Next, a urethane-based adhesive (same as above) was applied to the liquid crystal polyester film surface of the laminated film, and an LLDPE film having a thickness of 50 μm was bonded to obtain a back sheet. As a result of evaluating the weather resistance of the obtained laminated film by irradiating xenon from the white PET film side, shape change such as warping and tearing were not observed.
実施例３
厚さ２５０μｍの白色ＰＥＴフィルム（東レ（株）の「ルミラーＥ２０」：酸化チタン含有）の片面に、ウレタン系接着剤（三井武田ケミカル（株）：主剤「タケラックＡ５１１」／硬化剤「Ａ５０」＝１０／１（質量比））を塗布し、製造例１（２）で得られた液晶ポリエステルフィルムを貼り合わせ、積層フィルムを得た。次いで、この積層フィルムの液晶ポリエステルフィルム面に、ウレタン系接着剤（三井武田ケミカル（株）：主剤「タケラックＡ５１１」／硬化剤「Ａ５０」＝１０／１（質量比））を塗布し、製造例１（２）で得られた液晶ポリエステルフィルムを貼り合わせた。さらに、この積層フィルムの液晶ポリエステルフィルム面に、ウレタン系接着剤（同上）を塗布し、厚さ５０μｍのＬＬＤＰＥフィルムを貼り合わせ、積層フィルムを得た。得られた積層フィルムについて、白色ＰＥＴフィルム側からキセノン照射することにより、耐候性を評価した結果、反り等の形状変化や破れは見られなかった。 Example 3
A urethane adhesive (Mitsui Takeda Chemical Co., Ltd .: main agent “Takelac A511” / curing agent “A50”) on one side of a 250 μm thick white PET film (Tolu Co., Ltd. “Lumirror E20”: containing titanium oxide) = 10/1 (mass ratio)) was applied, and the liquid crystal polyester film obtained in Production Example 1 (2) was bonded to obtain a laminated film. Next, a urethane adhesive (Mitsui Takeda Chemical Co., Ltd .: main agent “Takelac A511” / curing agent “A50” = 10/1 (mass ratio)) is applied to the liquid crystal polyester film surface of this laminated film, and a production example The liquid crystal polyester film obtained in 1 (2) was bonded. Further, a urethane adhesive (same as above) was applied to the liquid crystal polyester film surface of the laminated film, and an LLDPE film having a thickness of 50 μm was bonded to obtain a laminated film. As a result of evaluating the weather resistance of the obtained laminated film by irradiating xenon from the white PET film side, shape change such as warping and tearing were not observed.
　１・・・有機ＥＬ素子、２・・・基板、３・・・封止材、４Ａ・・・陰極、４Ｂ・・・陽極、５・・・有機ＥＬ層、５ａ・・・電子輸送層、５ｂ・・・発光層、５ｃ・・・正孔輸送層、６・・・封止層、２１・・・ポリオレフィン層、２２・・・接着層、２３・・・液晶ポリエステル層、２４・・・水蒸気バリア層、２５・・・接着層、２６・・・白色顔料含有層。 DESCRIPTION OF SYMBOLS 1 ... Organic EL element, 2 ... Substrate, 3 ... Sealing material, 4A ... Cathode, 4B ... Anode, 5 ... Organic EL layer, 5a ... Electron transport layer, 5b ... light emitting layer, 5c ... hole transport layer, 6 ... sealing layer, 21 ... polyolefin layer, 22 ... adhesive layer, 23 ... liquid crystal polyester layer, 24 ... Water vapor barrier layer, 25 ... adhesive layer, 26 ... white pigment-containing layer.

Claims (12)

  1. 　液晶ポリエステル層の裏側に、白色顔料含有層が設けられてなる有機ＥＬ用基板。 An organic EL substrate in which a white pigment-containing layer is provided on the back side of the liquid crystal polyester layer.
  2. 　前記液晶ポリエステル層が、下記式（１）で表される繰返し単位と、下記式（２）で表される繰返し単位と、下記式（３）で表される繰返し単位とを有し、２，６－ナフチレン基を含む繰返し単位の含有量が、全繰返し単位の合計量に対して、４０モル％以上である液晶ポリエステルから構成される層である請求項１に記載の有機ＥＬ用基板。
    －Ｏ－Ａｒ1－ＣＯ－　　　　（１）
    －ＣＯ－Ａｒ2－ＣＯ－　　　（２）
    －Ｏ－Ａｒ3－Ｏ－　　　　　（３）
    （Ａｒ1は、２，６－ナフチレン基、１，４－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ2及びＡｒ3は、それぞれ独立に、２，６－ナフチレン基、１，４－フェニレン基、１，３－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ1、Ａｒ2又はＡｒ3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 layer has a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3), The organic EL substrate according to claim 1, wherein the organic EL substrate is a layer composed of a liquid crystal polyester in which the content of the repeating unit containing a 6-naphthylene group is 40 mol% or more based on the total amount of all the repeating units.
    —O—Ar 1 —CO— (1)
    —CO—Ar 2 —CO— (2)
    —O—Ar 3 —O— (3)
    (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.)
  3. 　前記液晶ポリエステル層の温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が、０．１ｇ／ｍ2・２４ｈ以下である請求項１に記載の有機ＥＬ用基板。 2. The organic EL substrate according to claim 1, wherein a water vapor permeability measured at a temperature of 40 ° C. and a relative humidity of 90% of the liquid crystal polyester layer is 0.1 g / m 2 · 24 h or less.
  4. 　前記液晶ポリエステル層の厚さが、５～５００μｍである請求項１に記載の有機ＥＬ用基板。 2. The organic EL substrate according to claim 1, wherein the liquid crystal polyester layer has a thickness of 5 to 500 μm.
  5. 　前記白色顔料含有層が、塩基性炭酸鉛、塩基性硫酸鉛、塩基性ケイ酸鉛、亜鉛華、硫化亜鉛、リトポン、三酸化アンチモン及び酸化チタンからなる群から選ばれる少なくとも１種の白色顔料を含む層である請求項１に記載の有機ＥＬ用基板。 The white pigment-containing layer includes at least one white pigment selected from the group consisting of basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, and titanium oxide. The organic EL substrate according to claim 1, wherein the organic EL substrate is a layer containing the organic EL substrate.
  6. 　前記白色顔料含有層が、ポリエステルを含む層である請求項１に記載の有機ＥＬ用基板。 The organic EL substrate according to claim 1, wherein the white pigment-containing layer is a layer containing polyester.
  7. 　前記液晶ポリエステル層の少なくとも一方の面上に、水蒸気バリア層が設けられている請求項１に記載の有機ＥＬ用基板。 The organic EL substrate according to claim 1, wherein a water vapor barrier layer is provided on at least one surface of the liquid crystal polyester layer.
  8. 　前記水蒸気バリア層が、アルミニウム、ケイ素、チタン、クロム、鉄、コバルト、ニッケル、銅、亜鉛、銀及び金からなる群から選ばれる少なくとも１種の元素の単体、前記元素の酸化物、前記元素の窒化物並びに前記元素の酸窒化物からなる群から選ばれる少なくとも１種の物質から構成される層である請求項７に記載の有機ＥＬ用基板。 The water vapor barrier layer is composed of at least one element selected from the group consisting of aluminum, silicon, titanium, chromium, iron, cobalt, nickel, copper, zinc, silver and gold, an oxide of the element, The organic EL substrate according to claim 7, which is a layer composed of at least one substance selected from the group consisting of a nitride and an oxynitride of the element.
  9. 　前記水蒸気バリア層の厚さが、５～２５０ｎｍである請求項７に記載の有機ＥＬ用基板。 The organic EL substrate according to claim 7, wherein the water vapor barrier layer has a thickness of 5 to 250 nm.
  10. 　前記液晶ポリエステル層の表側に、ポリオレフィン層が設けられている請求項１に記載の有機ＥＬ用基板。 The substrate for organic EL according to claim 1, wherein a polyolefin layer is provided on the front side of the liquid crystal polyester layer.
  11. 　前記ポリオレフィン層の厚さが、５～２００ｎｍである請求項１０に記載の有機ＥＬ用基板。 The organic EL substrate according to claim 10, wherein the polyolefin layer has a thickness of 5 to 200 nm.
  12. 　請求項１に記載の有機ＥＬ用基板と、前記有機ＥＬ用基板上に配置された一対の電極と、前記一対の電極間に配置された有機ＥＬ層とを有する有機ＥＬ素子。 An organic EL element comprising: the organic EL substrate according to claim 1; a pair of electrodes disposed on the organic EL substrate; and an organic EL layer disposed between the pair of electrodes.
PCT/JP2012/053387 2011-02-16 2012-02-14 Organic electroluminescent substrate, and organic electroluminescent element WO2012111662A1 (en)

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