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WO2016052312A1 - Substrat pour électroluminescence organique, et écran électroluminescent organique l'utilisant - Google Patents

Substrat pour électroluminescence organique, et écran électroluminescent organique l'utilisant Download PDF

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Publication number
WO2016052312A1
WO2016052312A1 PCT/JP2015/077021 JP2015077021W WO2016052312A1 WO 2016052312 A1 WO2016052312 A1 WO 2016052312A1 JP 2015077021 W JP2015077021 W JP 2015077021W WO 2016052312 A1 WO2016052312 A1 WO 2016052312A1
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Prior art keywords
polyimide
substrate
group
organic
solvent
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PCT/JP2015/077021
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English (en)
Japanese (ja)
Inventor
大樹 魚山
真 情野
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Central Glass Co Ltd
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Central Glass Co Ltd
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Priority claimed from JP2015180594A external-priority patent/JP2016076480A/ja
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to CN201580053679.3A priority Critical patent/CN106797683B/zh
Priority to KR1020177011959A priority patent/KR20170062528A/ko
Publication of WO2016052312A1 publication Critical patent/WO2016052312A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • H10K59/10—OLED displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to a substrate for organic electroluminescence (hereinafter sometimes referred to as EL) and an organic EL display using the same.
  • EL organic electroluminescence
  • Organic EL displays have been put into practical use as next-generation displays having features such as high contrast ratio, high response speed, wide viewing angle, and low power consumption.
  • efforts are being made to replace organic EL display substrates with conventional plastics that can be made thinner, lighter, and flexible.
  • the performance required for an organic EL substrate includes device surface leakage, surface flatness closely related to short circuit, and heat resistance and solvent resistance to such an extent that they are not damaged in the device fabrication process.
  • dimensional stability against temperature changes is also required to prevent defects in the organic layer and electrodes due to the expansion and contraction of the substrate.
  • transparency in the visible light region for extracting light from the substrate side is essential.
  • the substrate material having excellent transparency examples include polymethyl methacrylate, polycarbonate, and polyethersulfone.
  • the above materials have a low glass transition temperature and do not have sufficient heat resistance with respect to the process temperature for producing an organic EL element of about 250 ° C.
  • Polyimide is mentioned for organic EL excellent in heat resistance.
  • Polyimide is a fully aromatic polyimide using aromatic diamine and aromatic tetracarboxylic dianhydride as raw material, aliphatic polyimide using aliphatic diamine and aliphatic tetracarboxylic dianhydride or both as raw material Are distinguished.
  • the wholly aromatic polyimide a charge transfer interaction occurs between a portion derived from the raw material aromatic diamine and a portion derived from the aromatic tetracarboxylic dianhydride. As a result, it is excellent in heat resistance, solvent resistance, and mechanical strength. However, since it is generally colored in the visible light region, it is not used as a material for a transparent substrate.
  • Patent Document 1 and Patent Document 2 describe a transparent substrate using an aliphatic polyimide using an aliphatic tetracarboxylic dianhydride as a raw material.
  • polyimides with an aliphatic skeleton can achieve transparency in the visible light region, the glass transition temperature is lowered due to the flexible aliphatic skeleton, and the dimensional stability is lowered due to the increased thermal expansion coefficient. Occur. Therefore, in order to put it into practical use as a transparent substrate, further improvement in heat resistance is necessary.
  • Patent Documents 3 to 9 disclose polyimides having a hexafluoroisopropanol group (—C (CF 3 ) 2 OH, hereinafter sometimes referred to as HFIP group).
  • the present invention has excellent transparency in the visible light region after forming the substrate, organic solvent resistance, heat resistance, dimensional stability and mechanical strength.
  • An object of the present invention is to provide an organic EL substrate having both of the above in a balanced manner.
  • Patent Document 3 is excellent in solubility and moldability, there is no description regarding organic solvent resistance, heat resistance, thermal expansion coefficient, and mechanical properties in the polyimide molded body.
  • the polyimides described in Patent Documents 4 to 6 are excellent in solubility and heat resistance in the polyimide molded body, but there is no description regarding organic solvent resistance, heat resistance, thermal expansion coefficient, and mechanical properties.
  • the polyimide described in Patent Document 7 has no description regarding moldability, organic solvent resistance, heat resistance, thermal expansion coefficient, and mechanical properties in the polyimide molded body.
  • Patent Document 8 is excellent in solubility, transparency in a polyimide molded body, and heat resistance, there is no description regarding a thermal expansion coefficient and mechanical properties, and details regarding transparency are not described.
  • the polyimide described in Patent Document 9 is excellent in solubility and transparency in a polyimide molded body and exhibits a low thermal expansion coefficient. However, there is no description regarding mechanical properties and heat resistance, and details regarding transparency are not described. Further, there is no specific description regarding the use of the organic EL substrate for the polyimides described in Patent Documents 3 to 9.
  • the present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by using a polyimide resin composition containing at least a polyimide containing 50 mol% or more of a repeating unit represented by the following general formula (1), and completed the present invention.
  • R 1 is an ether bond, sulfide bond, sulfoxy bond, methylene group or ethylene group
  • R 2 and R 3 are each independently a hydrogen atom, methyl group or trifluoromethyl group
  • R 4 is (A tetravalent organic group containing an aromatic ring, which is represented by any of the following structures)
  • the present invention includes the following inventions.
  • substrate which consists of a molded object of the polyimide resin composition containing at least the polyimide which contains 50 mol% or more of repeating units represented by General formula (1).
  • R 1 is an ether bond, sulfide bond, sulfoxy bond, methylene group or ethylene group
  • R 2 and R 3 are each independently a hydrogen atom, methyl group or trifluoromethyl group
  • R 4 is (A tetravalent organic group containing an aromatic ring, which is represented by any of the following structures)
  • invention 2 The substrate for organic electroluminescence according to invention 1, comprising a molded body of a polyimide resin composition comprising only a polyimide having a repeating unit represented by the general formula (1).
  • invention 3 The substrate for organic electroluminescence according to invention 1 or 2, wherein the coefficient of thermal expansion at 30 to 250 ° C is 50 ppm / ° C or less.
  • invention 4 The substrate for organic electroluminescence according to any one of inventions 1 to 3, wherein the transmittance in a wavelength region of 420 to 780 nm is 60% or more.
  • invention 5 The substrate for organic electroluminescence according to any one of inventions 1 to 4, wherein R 1 is a methylene group, and R 2 and R 3 are each a hydrogen atom.
  • invention 7 An organic electroluminescence device comprising at least the organic electroluminescence substrate according to any one of inventions 1 to 6.
  • invention 8 An organic electroluminescence display comprising at least the organic electroluminescence substrate according to any one of inventions 1 to 6.
  • a bottom emission type organic electroluminescence display comprising at least the organic electroluminescence substrate according to any one of inventions 1 to 6.
  • a polyimide solution comprising a polyimide resin composition containing at least a polyimide containing 50 mol% or more of the repeating unit represented by the general formula (1), and an organic solvent.
  • R 1 is an ether bond, sulfide bond, sulfoxy bond, methylene group or ethylene group
  • R 2 and R 3 are each independently a hydrogen atom, methyl group or trifluoromethyl group
  • R 4 is (A tetravalent organic group containing an aromatic ring, which is represented by any of the following structures)
  • invention 13 The polyimide solution according to any one of inventions 10 to 12, wherein the organic solvent is at least one selected from the group consisting of an amide solvent, an ether solvent, an aromatic solvent, a halogen solvent, and a lactone solvent.
  • the organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, Cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, dioxane, trioxane, benzene, anisole, nitrobenzene, benzonitrile, chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, ⁇ -Butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone and ⁇ -methyl- ⁇ -but
  • invention 16 Applying the polyimide solution according to any one of Inventions 10 to 15 to a supporting substrate; Drying the applied polyimide solution to obtain a resin film; And a step of obtaining a polyimide molded body by subjecting the obtained resin film to a heat treatment.
  • invention 20 The method according to any one of inventions 17 to 19, wherein the molded body has a transmittance of 60% or more in a wavelength region of 420 to 780 nm.
  • the molded body is A polyimide solution containing a polyimide resin composition and an organic solvent is applied to a support substrate, The method according to any one of inventions 17 to 22, which is a polyimide molded body obtained by heat-treating a resin film obtained by drying the applied polyimide solution.
  • invention 24 24.
  • the organic solvent is at least one selected from the group consisting of an amide solvent, an ether solvent, an aromatic solvent, a halogen solvent and a lactone solvent.
  • the organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, Cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, dioxane, trioxane, benzene, anisole, nitrobenzene, benzonitrile, chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, ⁇ -Butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone and ⁇ -methyl- ⁇ -but
  • the organic EL refers to a phenomenon in which light is emitted by applying a voltage to an organic substance
  • the organic EL element includes white by combining organic materials that emit light in colors such as red, green, and blue.
  • the organic EL display refers to a display screen device using an organic EL element.
  • the polyimide resin composition according to the present invention has high solubility in a polar organic solvent, and can be applied to a supporting substrate in a polyimide solution state and molded on the supporting substrate.
  • the molded polyimide is excellent in transparency in the visible light region, has a good balance of organic solvent resistance, heat resistance, dimensional stability and mechanical strength, and is useful as a substrate for organic EL.
  • the polyimide resin composition according to the present invention includes at least a polyimide having a repeating unit represented by the following general formula (1), , Having a repeating unit represented by the following general formula (1) of 50 mol% or more, preferably 75 mol% or more, more preferably comprising only a repeating unit represented by the following general formula (1).
  • R 1 is an ether bond, a sulfide bond, a sulfoxy bond, a methylene group or an ethylene group
  • R 2 and R 3 are each independently a hydrogen atom, a methyl group or a trifluoromethyl group
  • R 4 is a tetravalent organic group containing an aromatic ring, and is represented by, for example, any one of the following structures. Among these, the following tetravalent organic groups are preferable. Among these, the following tetravalent organic groups are more preferable.
  • R 1 , R 2 and R 3 are derived from R 1 , R 2 and R 3 in the diamine compound represented by the general formula (8), respectively.
  • R 4 is derived from R 4 in the aromatic tetracarboxylic dianhydride represented by the general formula (10).
  • R 1 is preferably a methylene group, and R 2 and R 3 are each preferably a hydrogen atom. That is, the repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).
  • R 4 has the same meaning as R 4 in the general formula (1).
  • the polyimide according to the present invention may have a repeating unit other than the repeating unit represented by the general formula (1), and may have the repeating unit of 50 mol% or less, or 25 mol% or less. Is preferred. Moreover, the repeating unit of the said General formula (1) may be regularly arranged in the polyimide, and may exist at random. Examples of the repeating unit other than the repeating unit represented by the general formula (1) include, but are not limited to, repeating units represented by any of the following.
  • the weight average molecular weight of the polyimide according to the present invention is not particularly limited, but the lower limit may be 30,000, preferably 40,000, particularly preferably 50,000.
  • the upper limit may be 1,000,000, preferably 500,000, particularly preferably 200,000.
  • the polyimide according to the present invention may have a weight average molecular weight of 30,000 to 1,000,000, preferably 40,000 to 500,000, particularly preferably 50,000 to 200,000. If the weight average molecular weight is less than 30,000, the stability of the substrate after molding is poor and problems such as substrate cracking are likely to occur, and if it exceeds 1,000,000, the viscosity of the solution is high and difficult to mold. May be.
  • the said weight average molecular weight says the value of standard polystyrene conversion by a gel permeation chromatography (henceforth GPC).
  • the composition according to the present invention preferably contains at least a polyimide having 50% by mole or more of the repeating unit represented by the general formula (1), and is composed only of the polyimide.
  • the composition according to the present invention may contain other components in addition to the polyimide. When other components are included, the content may be 50 mol% or less, preferably 25 mol% or less, and more preferably 10 mol% or less.
  • Polyimide other than the polyimide which has a repeating unit represented by General formula (1) may be sufficient.
  • This polyimide is not particularly limited, and one or more known polyimides can be appropriately selected and used.
  • This polyimide may be a polyimide synthesized using “other diamine compound” described later or a tetracarboxylic dianhydride described later as a raw material.
  • the substrate for organic EL of the present invention (hereinafter sometimes simply referred to as “substrate of the present invention”) is a molded article of the polyimide resin composition according to the present invention. Since this polyimide molded body has a good balance of transparency, organic solvent resistance, heat resistance, dimensional stability and mechanical strength, it can be suitably used as an organic EL substrate.
  • a polyamic acid that is a polyimide precursor is coated on a support substrate, and then dehydrated by heating on the support substrate.
  • a polyimide molded body is obtained by polyimidation by a chemical reaction. Therefore, the change in the molecular structure due to the heat treatment on the supporting base material is large, cracks and repellency are likely to occur, and it is not easy to produce a uniform substrate with high flatness.
  • the substrate of the present invention since it can be formed on the support base material in the state of polyimide, the change in the molecular structure by heat treatment on the support base material is small, cracks and repellency hardly occur, It is easy to obtain a polyimide molded body (substrate) having a desired flatness and a uniform state. After molding, it is excellent in transparency, has both organic solvent resistance and heat resistance, and does not easily cause substrate defects in the device manufacturing process.
  • the substrate of the present invention can be suitably used for an organic EL display.
  • the organic EL substrate of the present invention can be preferably used, and a material having high light transmittance in the visible light region can be particularly preferably used.
  • the substrate of the present invention that is, the polyimide molded body according to the present invention will be described.
  • the polyimide molded body according to the present invention preferably has a transmittance (hereinafter sometimes referred to as T%) of 60% or more in a high visible wavelength region of 420 nm or more, that is, in a wavelength region of 420 to 780 nm.
  • T% transmittance
  • the transmittance is 60% or more in a full visible light region having a high wavelength of 400 nm or more, that is, a wavelength region of 400 to 780 nm.
  • Particularly preferred is 70% or more.
  • the cut-off frequency is preferably a short wavelength of 380 nm or less.
  • the upper limit of the thermal expansion coefficient (hereinafter sometimes referred to as CTE) of the polyimide molded body according to the present invention is preferably 30 ppm / ° C., more preferably 30 ppm / ° C. in the range of 30 to 250 ° C.
  • a lower limit is not specifically limited, 0.5 ppm / degreeC is preferable and 1 ppm / degreeC is more preferable.
  • 1 ppm / ° C. or higher and 50 ppm / ° C. or lower is preferable, and 5 ppm / ° C. or higher and 30 ppm / ° C. or lower is more preferable.
  • the dimensional stability is inferior, which may cause problems such as generation of cracks or unintended substrate peeling.
  • the glass transition temperature of the polyimide molded body according to the present invention (hereinafter sometimes referred to as Tg) is preferably 250 ° C. or higher from the viewpoint of heat resistance, and more preferably 300 ° C. or higher from the viewpoint of being able to cope with a high process temperature. preferable.
  • the glass transition temperature (Tg) refers to a value when measured under conditions of a heating rate of 10 ° C./min.
  • the thermal expansion coefficient (CTE) and glass transition temperature (Tg) can be measured by thermomechanical analysis (TMA) or the like.
  • the decomposition temperature of the polyimide molded body according to the present invention is 5% weight reduction temperature (hereinafter sometimes referred to as Td 5 ) as an index, and the 5% weight reduction temperature is preferably 300 ° C. or more, more preferably 350 ° C. or more.
  • Td 5 5% weight reduction temperature
  • the 5% weight loss temperature refers to a temperature at which a weight loss of 5% with respect to the initial weight was measured by thermogravimetry using a thermogravimetric analyzer.
  • the elastic modulus (tensile elastic modulus) of the polyimide molded body according to the present invention is preferably 1.0 GPa or more and 6.0 GPa or less, and more preferably 1.5 GPa or more and 5.0 GPa or less. If the elastic modulus is greater than 6.0 GPa, the substrate tends to warp after curing.
  • the maximum stress is preferably 70 MPa or more, and more preferably 100 MPa or more. If the tensile strength is less than 70 MPa, it is fragile and difficult to handle when used as an organic EL substrate.
  • the breaking elongation is preferably 5% or more, and more preferably 10% or more.
  • the elongation at break is less than 5%, the bending stress when the polyimide molded body is used as the substrate is weak, and the reliability of the substrate is lowered.
  • an organic EL substrate is an organic solvent used in an organic EL display manufacturing process, such as dimethylacetamide (DMAc), tetrahydrofuran (THF), acetone (acetone), ethyl acetate (EtOAc), isopropanol (IPA), It is preferable that the film is difficult to be immersed in a solvent such as toluene and hexane.
  • the polyimide according to the present invention is excellent in solubility in these organic solvents in the state before molding, but in the state after molding, that is, in the substrate of the present invention, the organic solvent resistance. Excellent in resistance to these organic solvents. Therefore, the polyimide according to the present invention can be easily molded by application with a solution, and the molded substrate, that is, the substrate of the present invention has resistance to organic solvents.
  • the thickness of the polyimide molded body according to the present invention is not particularly limited, but the lower limit may be 0.5 ⁇ m, preferably 1 ⁇ m, particularly preferably 10 ⁇ m.
  • the upper limit may be 500 ⁇ m, preferably 100 ⁇ m, particularly preferably 80 ⁇ m. It may be 0.5 to 500 ⁇ m, preferably 1 to 100 ⁇ m, particularly preferably 10 to 80 ⁇ m.
  • the manufacturing method of the polyimide which concerns on this invention is not specifically limited.
  • the polyimide according to the present invention can be produced according to the method for synthesizing a polyimide having an HFIP group described in Patent Document 6.
  • a diamine having an HFIP group represented by the following general formula (8) and a tetracarboxylic dianhydride represented by the following general formula (10) are essential raw materials and melted at 150 ° C. or higher. The method of letting it be mentioned.
  • This polycondensation reaction is preferably carried out at ⁇ 20 to 80 ° C., and the diamine and the tetracarboxylic dianhydride are preferably reacted in a one-to-one manner in a molar ratio.
  • R 1 and R 2 each have the same meanings as R 1 and R 2 in the general formula (1).
  • R 4 have the same meanings as in formula (1) R 4 in.
  • the organic solvent that can be used in the polycondensation reaction is not particularly limited as long as the raw material compound is dissolved.
  • the polyimide according to the present invention can be obtained by further dehydrating and ring-closing the polyamic acid obtained by the condensation polymerization reaction.
  • This dehydration cyclization reaction is performed under conditions such as a heating method and a chemical method that promote cyclization.
  • the heating method the polyamic acid immediately after polymerization is imidized by heating at a high temperature of 150 to 250 ° C., and in the chemical method, a base such as pyridine or triethylamine and acetic anhydride are respectively added to the starting diamine at room temperature (0 to 50 ° C.).
  • the polyimide solution according to the present invention can be obtained by imidization by adding 2 molar equivalents or more and less than 10 equivalents.
  • the concentration of polyimide in this solution is preferably 5% by mass or more and 50% by mass or less. If it is less than 5% by mass, it is not industrially practical. If it exceeds 50% by mass, it is difficult to dissolve. Furthermore, it is preferably 10% by mass or more and 40% by mass or less.
  • the thus obtained polyimide solution according to the present invention can be used as it is for the production of the substrate of the present invention, that is, for the production of the polyimide molded body according to the present invention.
  • the polyimide solution according to the present invention is added to a poor solvent such as water or alcohol, and the polyimide is precipitated.
  • a polyimide solution may be prepared again by dissolving in an organic solvent so as to have the above concentration, and the prepared solution may be used for production of the polyimide molded body according to the present invention.
  • the organic solvent is not particularly limited as long as the polyimide according to the present invention is dissolved, and examples thereof include the same types of organic solvents as mentioned in the organic solvent that can be used for the condensation polymerization reaction. Alternatively, two or more kinds of mixed solvents may be used.
  • a diamine having an HFIP group represented by the general formula (8) is used as one of the raw material compounds.
  • HFIP-MDA diamine represented by the formula (9)
  • the diamine having the HFIP group represented by the general formula (8) and other diamine compounds (hereinafter, other (Sometimes called a diamine compound).
  • the amount of the other diamine compound used is 5% or more and 50% or less, preferably 10% or more and 30% or less, expressed as mass% with respect to the weight of the entire diamine.
  • a part of hydrogen atoms of the aromatic ring of the diamine may be substituted with a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, an HFIP group, a hydroxy group, or a cyano group. . Moreover, these may be used independently and can also be used together 2 or more types.
  • a tetracarboxylic dianhydride represented by the general formula (10) is used as one of the raw material compounds.
  • benzene-1,2,4,5-tetracarboxylic dianhydride (hereinafter sometimes referred to as PMDA), 3,6-bis (trifluoromethyl) benzene-1,2,4, 5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes referred to as BPDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic acid Anhydride (hereinafter sometimes referred to as 6FDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter sometimes referred to as BTDA), 4,4′-oxydiphthalic dianhydride Product (hereinafter sometimes referred to as ODPA), thiophene-2,3,4,5-tetracarboxylic dianhydride, and the like. These may be used alone or in combination of two or more.
  • PMDA benzene-1,
  • PMDA, BPDA, BTDA, 6FDA or ODPA is preferable from the viewpoint of availability, and 6FDA or ODPA is particularly preferable because of transparency of the obtained polyimide in the visible light region.
  • the polyimide molded body according to the present invention can be obtained by heat-treating the composition according to the present invention. Specifically, a step of applying a solution containing the composition according to the present invention (a solution in which the composition according to the present invention is dissolved in the organic solvent) to a supporting substrate (coating step), removing and drying the solvent. It can be obtained through a step (solvent removal step) and a step of further heat-treating the obtained resin film (heating step).
  • the coating method used in the coating step is not particularly limited, and a known method can be adopted. Depending on the desired coating thickness, resin viscosity, etc., known coating devices such as a spin coater, bar coater, doctor blade coater, air knife coater, roll coater, rotary coater, flow coater, die coater, lip coater and the like can be used as appropriate.
  • the support substrate is not particularly limited.
  • glass, silicon wafer, stainless steel, alumina, copper, nickel and other inorganic base materials polyethylene terephthalate, polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polypropylene
  • the organic base material include polyether sulfone, polyethylene terephthalate, polyphenylene sulfone, and polyphenylene sulfide. From the viewpoint of heat resistance, it is preferable to use an inorganic base material such as glass, a silicon wafer, and stainless steel.
  • the thickness of the coating film containing the composition according to the present invention can be appropriately adjusted depending on the concentration of the resin polyimide component in the solution containing the composition according to the present invention, and usually 1 ⁇ m or more, 1000 ⁇ m or less, preferably 5 ⁇ m or more and 500 ⁇ m or less. If the coating film is thinner than 1 ⁇ m, sufficient strength cannot be obtained for the substrate after molding, and if it is thicker than 1000 ⁇ m, defects such as repellency, dents, cracks and the like of the substrate occur, and a uniform substrate cannot be obtained.
  • the coating film by the coating process After obtaining the coating film by the coating process, it further undergoes a solvent removal process for removing and drying the solvent from the coating film, and a heating process for obtaining a polyimide molded body by heat-treating and curing the dried coating film (resin film).
  • a solvent removal process for removing and drying the solvent from the coating film
  • a heating process for obtaining a polyimide molded body by heat-treating and curing the dried coating film (resin film).
  • the temperature at which the solvent is removed and dried in the solvent removal step depends on the type of the organic solvent in which the composition according to the present invention is dissolved, but is preferably 50 ° C or higher and 220 ° C or lower, preferably 80 ° C or higher, 200 ° C. More preferably, it is not higher than ° C. If it is lower than 50 ° C., drying is insufficient, and if it is higher than 220 ° C., rapid solvent evaporation occurs, causing defects such as repellency, dents, cracks, etc., and a uniform film cannot be obtained.
  • the resin film can be cured by heat treatment at a high temperature to obtain the polyimide molded body according to the present invention.
  • this step removal of the residual solvent that could not be removed in the solvent removal step, improvement in the imidization rate, and improvement in physical properties are also expected.
  • the temperature at which the resin film is heated and cured is preferably 150 ° C. or higher and 400 ° C. or lower, more preferably 200 ° C. or higher and 300 ° C. or lower. If the temperature is lower than 150 ° C., the solvent may remain. If the temperature is higher than 400 ° C., defects such as cracks occur in the obtained organic EL substrate.
  • the heating step is preferably performed using an inert gas oven, a hot plate, a box dryer, or a conveyor dryer, but is not limited to the use of these devices.
  • the heating step is preferably performed under an inert gas stream from the viewpoint of preventing oxidation of the resin film and removing the solvent.
  • the inert gas include nitrogen and argon.
  • the flow rate of the inert gas is preferably 1 L / min or more and 5 L / min or less. If the flow rate of the inert gas is slower than 1 L / min, solvent removal and resin film curing may be insufficient. If it is faster than 5 L / min, only the resin film surface is dried, causing cracks and the like. Sometimes.
  • the heating time in the solvent removal step and the heating step is usually 0.5 hours or more and 3 hours or less, and each step can be performed continuously or separately.
  • the substrate of the present invention can be peeled off from the support substrate to produce a device, but advanced technology is required to fix it to a new support substrate, and the number of steps increases. It is desirable to produce a device for an organic EL substrate in a state of a molded body that is fixed to a supporting base without being peeled, and then manufacture a device.
  • the organic EL element of the present invention includes at least the substrate of the present invention, and other configurations are not particularly limited.
  • the organic EL element of the present invention may be an organic EL element using the substrate of the present invention as the substrate in an organic EL element comprising at least an organic light emitting layer, an electrode layer, and a substrate.
  • the organic EL device of the present invention includes a hole injection layer, a hole transport layer, a hole block layer, an electron transport layer, an electron injection layer, a desiccant, a sealing material, a metal plate, a filter layer, and a color.
  • a conversion phosphor layer (CCM layer), a passivation layer, a planarization layer, and the like may be provided.
  • Organic EL display of the present invention is provided with at least the substrate of the present invention, and other configurations are not particularly limited.
  • the organic EL display of the present invention may include the organic EL element of the present invention.
  • Thermal expansion coefficient and the glass transition temperature (hereinafter sometimes referred to as Tg) were obtained by conducting a tensile test using a model name “Thermo Plus EvoII TMA8310” manufactured by Rigaku Corporation.
  • Thermal decomposition temperature was measured by Rigaku Corporation, model name “RIGAKU Thermo Plus TG8310”.
  • Mechanical properties such as elastic modulus, stress, and elongation at break were determined by conducting a tensile test with an autograph 'Autograph AG-IS', a precision universal testing machine manufactured by Shimadzu Corporation.
  • Solvent solubility was determined by visual agitation using the model name 'UNI THERMO SHAKER NTS-1300', a constant temperature shaking water tank manufactured by Tokyo Rika Kikai Co., Ltd., with constant shaking in a water bath at a shaking speed of 100 rpm for the following time. It confirmed with and without the solid substance. Those that dissolve within 1 hour at 30 ° C. are good, those that dissolve within 1 hour at 70 ° C. are soluble, and those that do not dissolve within 1 hour at 70 ° C. are insoluble.
  • Example 1 In a 500 mL three-necked flask equipped with a nitrogen inlet tube and a stirring blade, HFIP-MDA, 58.3 g (110 mmol), 6FDA, 48.9 g (110 mmol), dimethylacetamide (hereinafter referred to as the chemical structure) shown in the following reaction formula, are shown. 220g), and the mixture was stirred at 20 ° C. under a nitrogen atmosphere to carry out the following reaction. To the obtained reaction solution, pyridine, 34.8 g (440 mmol), acetic anhydride, 44.9 g (440 mmol) were added in this order, and the mixture was further stirred for 24 hours. A solution was made.
  • a polyimide (A) substrate (polyimide (A) molded body) was prepared by applying a DMAc solution of polyimide (A) to a glass substrate, followed by drying and heat treatment. First, a DMAc solution of polyimide (A) is dropped on a glass substrate, and the spin coater is used to raise the rotation speed to 600 rpm over 10 seconds, and then held at the rotation speed of 600 rpm for 10 seconds. The DMAc solution was applied uniformly. After drying at 180 ° C. for 30 minutes in a nitrogen atmosphere to remove the solvent, and further heat-treating at 250 ° C.
  • a polyimide (A) substrate (polyimide ( A shaped product A) was obtained.
  • the thickness was measured with a film thickness meter (manufactured by Nikon Corporation, model name “DIGIMICRO MH-15”), it was 50 ⁇ m.
  • the solvent solubility test sample (precipitate in Example 1) was prepared by slowly pouring the polyimide (A) DMAc solution, 30 g, into a mixed solution of water, 90 g, methanol, 30 g to precipitate the polyimide (A).
  • the solvent solubility test sample was prepared by slowly pouring the polyimide (A) DMAc solution, 30 g, into a mixed solution of water, 90 g, methanol, 30 g to precipitate the polyimide (A).
  • each chemical structure is represented by the following reaction formula: HFIP-MDA, 58.3 g (110 mmol), BPDA, 32.4 g (110 mmol), DMAc as a solvent, 220 g And stirred at 20 ° C. in a nitrogen atmosphere to carry out the reaction shown below.
  • reaction solution 34.8 g (440 mmol) of pyridine and 44.9 g (440 mmol) of acetic anhydride were added in this order, and the mixture was further stirred for 24 hours, imidized, and then filtered under pressure.
  • a DMAc solution of polyimide (B) was prepared.
  • a part of the DMAc solution of polyimide (B) was used for the preparation of a solvent solubility test sample, and the rest was used for preparation of a polyimide (B) substrate (molded body of polyimide (B)).
  • the polyimide (B) substrate (molded body of polyimide (B)) was prepared by applying a DMAc solution of polyimide (B) to a glass substrate, followed by drying and heat treatment. First, a DMAc solution of polyimide (B) was dropped on a glass substrate, and the rotation speed was increased to 800 rpm over 10 seconds using a spin coater, and then held at a rotation speed of 800 rpm for 10 seconds. The solution was applied uniformly. In a nitrogen atmosphere, the solvent is removed by drying at 180 ° C. for 30 minutes, and after further heat treatment at 200 ° C.
  • the solvent solubility test sample (precipitate in Example 2) was prepared by slowly pouring the above-mentioned polyimide (B) in DMAc solution, 30 g into a mixed solution of water, 90 g, methanol and 30 g to precipitate polyimide (B). was dried at 100 ° C. for 8 hours in a nitrogen atmosphere.
  • Example 3 In a three-necked flask with a capacity of 500 mL equipped with a nitrogen introduction tube and a stirring blade, HFIP-MDA, 58.3 g (110 mmol), ODPA, 34.1 g (110 mmol), DMAc, 160 g, whose chemical structures are shown in the following reaction formula, were added. In addition, the mixture was stirred at 20 ° C. in a nitrogen atmosphere to carry out the following reaction. Pyridine, 34.8 g (440 mmol), acetic anhydride, 44.9 g (440 mmol) were sequentially added to the resulting reaction solution, and the mixture was further stirred for 24 hours to perform imidization.
  • the DMAc solution of polyimide (C) was produced by carrying out pressure filtration.
  • Part of the DMAc solution of polyimide (C) was used for the preparation of a solvent solubility test sample, and the rest was used for the preparation of a polyimide (C) substrate (polyimide (C) molded body).
  • the polyimide (C) substrate (molded body of polyimide (C)) was prepared by applying a DMAc solution of polyimide (C) to a glass substrate, followed by drying and heat treatment. First, a DMAc solution of polyimide (C) is hung on a glass substrate, and the spin coater is used to increase the rotation speed to 700 rpm over 10 seconds, and then the rotation speed is maintained at 700 rpm for 10 seconds. The DMAc solution was applied uniformly. After drying at 180 ° C. for 30 minutes in a nitrogen atmosphere, removing the solvent, and further heat-treating at 200 ° C. for 2 hours, cooling, and removing the polyimide film from the glass substrate, a polyimide (C) substrate (polyimide ( C) was obtained. It was 49 micrometers when thickness was measured with the said film thickness meter.
  • the solvent solubility test sample (precipitate in Example 3) was prepared by slowly pouring the polyimide (C) DMAc solution, 30 g, into a mixed solution of water, 90 g, methanol, and 30 g to precipitate the polyimide (C).
  • the solvent solubility test sample was prepared by slowly pouring the polyimide (C) DMAc solution, 30 g, into a mixed solution of water, 90 g, methanol, and 30 g to precipitate the polyimide (C).
  • the DMAc solution of polyimide (D) was produced by carrying out pressure filtration.
  • a part of the DMAc solution of polyimide (D) was used for the preparation of a solvent solubility test sample, and the rest was used for preparation of a polyimide (D) substrate (molded body of polyimide (D)).
  • a polyimide (D) substrate (polyimide (D) molded body) was prepared by applying a DMAc solution of polyimide (D) to a glass substrate, followed by drying and heat treatment.
  • a DMAc solution of polyimide (D) is hung on a glass substrate, and the spin coater is used to increase the rotation speed to 400 rpm over 10 seconds, and then held at a rotation speed of 300 rpm for 40 seconds.
  • the DMAc solution was applied uniformly.
  • the solvent is removed by drying at 180 ° C. for 30 minutes, and after further heat treatment at 200 ° C. for 2 hours, the polyimide film is removed from the glass substrate by cooling and removing the polyimide film from the glass substrate (polyimide (D ) Was obtained. It was 51 micrometers when thickness was measured with the said film thickness meter.
  • the solvent solubility test sample (precipitate in Example 4) was prepared by gradually pouring the above-mentioned polyimide (D) DMAc solution, 30 g, into a mixed solution of water, 90 g, methanol and 30 g to precipitate the polyimide (D). This was prepared by drying at 100 ° C. for 8 hours in a nitrogen atmosphere.
  • a polyimide (E) substrate (polyimide (E) molded body) was prepared by applying a DMAc solution of polyimide (E) to a glass substrate, followed by drying and heat treatment.
  • a DMAc solution of polyimide (E) is hung on a glass substrate, and the spin coater is used to raise the rotation speed to 550 rpm over 10 seconds, and then held at the rotation speed of 550 rpm for 10 seconds.
  • the DMAc solution was applied uniformly.
  • the solvent is removed by drying at 180 ° C. for 30 minutes, and after further heat treatment at 250 ° C. for 2 hours, the polyimide film is removed from the glass substrate by cooling and removing the polyimide film from the glass substrate (polyimide (E ) Was obtained. It was 49 micrometers when thickness was measured with the said film thickness meter.
  • a polyimide (F) substrate (polyimide (F) molded body) was prepared by applying a DMAc solution of polyimide (F) to a glass substrate, followed by drying and heat treatment.
  • a DMAc solution of polyimide (F) was dropped on a glass substrate, and the spin coater was used to raise the rotation speed to 650 rpm over 10 seconds, and then held at the rotation speed of 650 rpm for 10 seconds.
  • the DMAc solution was applied uniformly.
  • the solvent was removed by drying at 180 ° C. for 30 minutes, and after further heat treatment at 250 ° C. for 2 hours, the polyimide film was removed from the glass substrate by cooling and removing the polyimide film from the glass substrate (polyimide (F ) Was obtained.
  • the film thickness was measured with the film thickness meter, it was 38 ⁇ m.
  • a polyimide (G) substrate (polyimide (G) molded body) was prepared by applying a DMAc solution of polyimide (G) to a glass substrate, followed by drying and heat treatment. First, a DMAc solution of polyimide (G) was dropped on a glass substrate, and the spin coater was used to raise the rotation speed to 400 rpm over 10 seconds, and then held at the rotation speed of 400 rpm for 10 seconds. The DMAc solution was applied uniformly. In a nitrogen atmosphere, the solvent was removed by drying at 180 ° C. for 30 minutes, followed by heat treatment at 250 ° C. for 2 hours, followed by cooling and peeling off the polyimide film from the glass substrate to obtain a polyimide (G) substrate (polyimide (G ) Was obtained. It was 52 micrometers when thickness was measured with the said film thickness meter.
  • a polyimide (H) substrate (polyimide (H) molded body) was prepared by applying a DMAc solution of polyimide (H) to a glass substrate, followed by drying and heat treatment.
  • a DMAc solution of polyimide (H) was dropped on a glass substrate, and the spin coater was used to raise the rotation speed to 700 rpm over 10 seconds, and then held at the rotation speed of 700 rpm for 10 seconds.
  • the DMAc solution was applied uniformly.
  • the solvent was removed by drying at 180 ° C. for 30 minutes, and after further heat treatment at 250 ° C. for 2 hours, the polyimide film was removed from the glass substrate by cooling and removing the polyimide film from the glass substrate (polyimide (H ) Was obtained. It was 51 micrometers when thickness was measured with the said film thickness meter.
  • Table 1 shows the physical property evaluation results of the substrates of Examples 1 to 5, Comparative Examples 1 to 3, and Reference Example 1.
  • the main chain skeleton of the polyimide is the same, but the diamine used as a raw material is different. That is, as shown below, only diamine having HFIP groups (HFIP-MDA) is used in Example 1, and diamines having HFIP groups (HFIP-MDA) and HFIP groups are used in Examples 4 to 5 and Comparative Example 2.
  • HFIP-MDA diamine having HFIP groups
  • HFIP-MDA diamines having HFIP groups
  • a diamine (MDA) having no HFIP group was used in Comparative Example 3 in combination with a diamine (MDA) having no HFIP group:
  • the light transmittances at 400 nm and 420 nm of Examples 1, 4 to 5 and Comparative Examples 2 to 3 are higher as the content of HFIP groups is higher, and Examples using only HFIP-MDA having HFIP groups as a raw material diamine 1 was the highest.
  • the substrates of Examples 1 and 2 had a light transmittance at 400 nm, which was comparable to the substrate of Reference Example 1.
  • the substrate of Example 3 was superior to the substrate of Reference Example 1 in light transmittance at 400 nm.
  • the substrates of Examples 4 to 5 had a light transmittance at 400 nm lower than that of the substrate of Reference Example 1, but had sufficient transparency to be used as an organic EL substrate.
  • the cut-off wavelength of the substrates of Examples 1 to 5 is higher than that of Reference Example 1, but is sufficiently transparent to be used as a substrate for an organic EL display because it has high transparency in the visible light region of 400 nm or more. Transparency.
  • the substrates of Examples 1 to 3 exhibited higher Tg than the substrate of Reference Example 1, and among them, the substrates of Examples 1 to 2 exhibited particularly high Tg.
  • the substrates of Examples 4 to 5 exhibited a lower Tg than the substrate of Reference Example 1, but had sufficient heat resistance for use as an organic EL substrate. Although Td 5 of the substrates of Examples 1 to 5 was lower than Td 5 of the substrate of Reference Example 1, it had sufficient heat resistance for use as an organic EL substrate.
  • the substrates of Examples 1 to 5 had a lower CTE than the substrate of Reference Example 1, and were excellent in dimensional stability against temperature changes.
  • the substrate of Comparative Example 1 exhibited a CTE as high as the substrate of Reference Example 1.
  • the substrate of Example 1 had higher tensile stress than the substrate of Reference Example 1.
  • the substrates of Examples 2 to 5 had lower mechanical stress than the substrate of Reference Example 1, but had sufficient mechanical strength to be used as an organic EL substrate.
  • the elastic modulus of the substrates of Examples 1 to 2 and 4 showed the same value as the elastic modulus of the substrate of Reference Example 1, but the elastic modulus of the substrate of Example 3 was higher than the elastic modulus of the substrate of Reference Example 1. It was excellent.
  • the breaking elongation of the substrates of Examples 1 to 5 was lower than that of the substrate of Reference Example 1, but had sufficient tensile strength for use as an organic EL substrate.
  • FIG. 1 shows the measurement results of the light transmission spectra of the substrates produced in Examples 1, 4 to 5 and Comparative Examples 2 to 3.
  • solvent solubility test The solvent solubility test was conducted using the samples for the solvent solubility test of polyimides (A) to (D) prepared in Examples 1 to 3 and Comparative Example 1 (polyimides (A) to (D) before molding) and the substrate. Eight types of (polyimides (A) to (D) after molding) were performed.
  • test specimen Put the test specimen and the solvent shown in Table 2 (DMAc, THF, acetone, ethyl acetate, isopropyl alcohol, toluene or hexane) into a bottle that can be capped with a screw type, and adjust the concentration to 10% by mass after dissolution.
  • the solution was sealed and stirred using a vibration stirrer to evaluate the solubility.
  • polyimides (A) to (D) before molding showed good solubility in aprotic polar solvents such as DMAc, THF, acetone, and ethyl acetate.
  • the polyimides (A) to (D) were insoluble.
  • polyimides (B) to (D) before molding and polyimides (A) to (D) after molding were insoluble, whereas before molding, The polyimide (A) showed solubility. None of the polyimides (A) to (D) was insoluble in nonpolar solvents such as toluene and hexane.
  • the polyimides (A) to (D) are dissolved in the aprotic polar solvent before molding, but are insoluble after molding, and thus have excellent moldability before molding. It was shown to have resistance to organic solvents after molding. Since the polyimide (A) is also dissolved in the protic polar solvent, it was shown that the polyimide (A) has more excellent moldability.
  • the molded polyimides (A) to (D) were insoluble in all the solvents tested, they have a solvent resistance that does not damage the organic EL device manufacturing process.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un substrat pour électroluminescence organique caractérisé en ce qu'il comprend un article moulé d'une composition de résine de polyimide comprenant au moins un polyimide qui comprend au moins 50 % en moles de motifs constitutifs représentés par la formule générale (1) (dans la formule générale (1) : R1 représente une liaison éther, une liaison sulfure, une liaison sulfoxyde, un groupe méthylène ou un groupe éthylène ; R2 et R3 représentent chacun indépendamment un atome d'hydrogène, un groupe méthyle ou un groupe trifluorométhyle ; et R4 est un groupe organique tétravalent comprenant un cycle aromatique, et est représenté par l'une quelconque des structures suivantes). En plus d'être apte à être facilement moulé par son application sous forme de revêtement d'une solution, le substrat, après avoir été moulé, atteint une excellente transparence présentant peu de défauts de surface, et un excellent équilibre entre résistance aux solvants organiques, résistance à la chaleur, stabilité dimensionnelle et résistance mécanique.
PCT/JP2015/077021 2014-10-02 2015-09-25 Substrat pour électroluminescence organique, et écran électroluminescent organique l'utilisant Ceased WO2016052312A1 (fr)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JP2007119503A (ja) * 2004-10-13 2007-05-17 Central Glass Co Ltd 含フッ素重合性単量体及びそれを用いた高分子化合物
WO2010053185A1 (fr) * 2008-11-10 2010-05-14 味の素株式会社 Composition de résine pour carte de circuit imprimés
WO2012165455A1 (fr) * 2011-05-30 2012-12-06 セントラル硝子株式会社 Membrane de séparation des gaz
WO2013191180A1 (fr) * 2012-06-19 2013-12-27 新日鉄住金化学株式会社 Dispositif d'affichage, son procédé de fabrication, film de polyimide pour les bases de support de dispositif d'affichage, et procédé de fabrication d'un film de polyimide pour les bases de support de dispositif d'affichage
WO2014084185A1 (fr) * 2012-11-28 2014-06-05 セントラル硝子株式会社 Diamine contenant un groupe hexafluoroisopropanol, polyimide et polyamide l'utilisant, produit cyclisé à base de celle-ci et son procédé de production
JP2014127392A (ja) * 2012-12-27 2014-07-07 Denki Kagaku Kogyo Kk 有機ｅｌ装置用樹脂組成物及び有機ｅｌ装置
JP2014125455A (ja) * 2012-12-27 2014-07-07 Central Glass Co Ltd 含フッ素非対称ジアミン化合物を用いた高分子化合物とその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007119503A (ja) * 2004-10-13 2007-05-17 Central Glass Co Ltd 含フッ素重合性単量体及びそれを用いた高分子化合物
WO2010053185A1 (fr) * 2008-11-10 2010-05-14 味の素株式会社 Composition de résine pour carte de circuit imprimés
WO2012165455A1 (fr) * 2011-05-30 2012-12-06 セントラル硝子株式会社 Membrane de séparation des gaz
WO2013191180A1 (fr) * 2012-06-19 2013-12-27 新日鉄住金化学株式会社 Dispositif d'affichage, son procédé de fabrication, film de polyimide pour les bases de support de dispositif d'affichage, et procédé de fabrication d'un film de polyimide pour les bases de support de dispositif d'affichage
WO2014084185A1 (fr) * 2012-11-28 2014-06-05 セントラル硝子株式会社 Diamine contenant un groupe hexafluoroisopropanol, polyimide et polyamide l'utilisant, produit cyclisé à base de celle-ci et son procédé de production
JP2014127392A (ja) * 2012-12-27 2014-07-07 Denki Kagaku Kogyo Kk 有機ｅｌ装置用樹脂組成物及び有機ｅｌ装置
JP2014125455A (ja) * 2012-12-27 2014-07-07 Central Glass Co Ltd 含フッ素非対称ジアミン化合物を用いた高分子化合物とその製造方法

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