WO2022181351A1 - 積層体、表示装置、および表示装置の製造方法 - Google Patents
積層体、表示装置、および表示装置の製造方法 Download PDFInfo
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- WO2022181351A1 WO2022181351A1 PCT/JP2022/005307 JP2022005307W WO2022181351A1 WO 2022181351 A1 WO2022181351 A1 WO 2022181351A1 JP 2022005307 W JP2022005307 W JP 2022005307W WO 2022181351 A1 WO2022181351 A1 WO 2022181351A1
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- cured resin
- electrode
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- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZSOVVFMGSCDMIF-UHFFFAOYSA-N trimethoxy(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](OC)(OC)OC)=CC=CC2=C1 ZSOVVFMGSCDMIF-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/18—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/3665—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties specially adapted for use as photomask
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
- C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- 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
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- 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
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
-
- 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
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
-
- 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
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
-
- 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
- H10K59/12—Active-matrix OLED [AMOLED] displays
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
Definitions
- the present invention relates to a laminate, a display device, and a method for manufacturing a display device.
- organic electroluminescence (hereinafter referred to as “organic EL”) display device After forming a partition pattern on a substrate, the openings between the partitions are coated with a light emitting material, a hole transport material, an electron A method of forming an organic EL display device having a functional layer by dropping a functional material solution such as a transport material is known.
- organic EL organic electroluminescence
- an organic EL display device has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, and between the facing first and second electrodes, Light can be emitted by applying a voltage.
- a photosensitive resin composition that can be patterned by ultraviolet irradiation is generally used as the flattening layer material and the insulating layer material.
- a photosensitive resin composition using a polyimide resin or a polybenzoxazole resin has high heat resistance of the resin and little gas component generated from the cured product, so that a highly durable organic EL display device can be provided. (Patent Document 1).
- the functional layer is formed by the inkjet method
- the openings between the partition walls need to have good wettability with ink.
- Patent Document 2 a method has been studied in which the upper layer surface of the partition pattern on the substrate is subjected to a fluorination treatment by plasma irradiation to develop liquid repellency.
- a method of forming partition walls from a photosensitive resin composition containing an alkali-soluble resin and a liquid-repellent compound is being studied.
- a resist composition containing a fluorine-based acrylic polymer (Patent Document 3) and a photosensitive resin composition containing polysiloxane having a fluorinated alkyl group (Patent Document 4) are being studied.
- the liquid-repellent component also adheres to the openings between the partition walls due to the fluorination treatment, resulting in insufficient ink wettability at the openings.
- Patent Documents 3 and 4 have sufficient liquid repellency, and pattern formation is possible as a photosensitive resin composition.
- the fluorine-based acrylic polymer of Patent Document 3 is inferior in UV ozone resistance, and the liquid repellency of the upper surface of the partition wall is insufficient after UV ozone treatment.
- the fluorine atom-containing polysiloxane of Patent Document 4 is excellent in UV ozone resistance and can impart sufficient liquid repellency to the upper surface of the partition wall after UV ozone treatment.
- the cured product has a high water absorbency, and there is a problem in durability when it is used for a partition wall of a display device.
- an object of the present invention is to obtain a laminate that includes a resin cured product having high liquid repellency after UV ozone treatment and that has high durability when used in a display device.
- the present invention has the following configuration.
- the laminate of the present invention is A laminated body in which a substrate, a first electrode patterned on the substrate, and a cured resin material are laminated in this order, and at least a part of the cured resin material on the first electrode is open, A laminate that satisfies the properties (i) and (ii) in the analysis of the cured resin by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the concentration of F atoms of the cured resin material measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin material are in contact is 8.1 atom % or more and 30.0 atom % or less; and , the concentration of Si atoms is 1.0 atom % or more and 6.0 atom % or less; , the concentration of F atoms in the cured resin is 0.1 atom% or more and 8.0 atom% or less, measured in any range of 100 to 200 nm from the interface where the first electrode and the cured resin are in contact.
- the present invention it is possible to obtain a laminate that is provided with a resin cured product having high liquid repellency after UV ozone treatment and that has high durability when used in a display device.
- FIG. 1 is a schematic diagram of a laminate used for evaluation in Examples.
- FIG. 1 is a schematic diagram of a partition pattern 12 used for evaluation in Examples.
- FIG. 1 is a schematic diagram of a partition pattern 12 used for evaluation in Examples.
- FIG. It is a schematic diagram of a cross section of an example of a laminate.
- FIG. 4 is a schematic cross-sectional view of another example of a laminate; 10 is a C1s spectrum of XPS analysis in Example 7.
- FIG. 10 is a C1s spectrum of XPS analysis in Comparative Example 5.
- FIG. 10 is a C1s spectrum of XPS analysis in Example 11.
- FIG. 10 is a C1s spectrum of XPS analysis in Example 12.
- FIG. 13 is a C1s spectrum of XPS analysis in Example 13.
- FIG. 14 is a C1s spectrum of XPS analysis in Example 14.
- FIG. 10 is a C1s spectrum of XPS analysis in Example 16.
- FIG. 10 is a C
- the laminate of the present invention is a laminate in which a substrate, a first electrode patterned on the substrate, and a cured resin material are laminated in this order, and at least a part of the cured resin material on the first electrode is open. being a body, Analysis of the cured resin by X-ray photoelectron spectroscopy (XPS) provides a laminate that satisfies the properties (i) and (ii).
- XPS X-ray photoelectron spectroscopy
- the concentration of F atoms of the cured resin material measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin material are in contact is 8.1 atom % or more and 30.0 atom % or less; and , the concentration of Si atoms is 1.0 atom % or more and 6.0 atom % or less.
- the concentration of F atoms in the resin cured product measured in any range of 200 nm is 0.1 atom % or more and 8.0 atom % or less.
- the cured resin material of the laminate of the present invention has the characteristic (i) as the surface characteristic, and the characteristic (ii) inside the cured resin material. Due to such compositional characteristics, the laminate of the present invention is provided with a resin cured product having high liquid repellency after UV ozone treatment, and is excellent in durability when used in a display device.
- the characteristic (i) is measured from at least part of the surface of the cured resin on the side opposite to the interface where the first electrode and the cured resin are in contact. Moreover, it is preferable to measure within a range of 100 ⁇ m from the end of the opening of the cured resin. By measuring this range, the liquid repellency of the cured resin surface to the functional ink can be analyzed.
- the concentration of F atoms is 8.1 atom % or more and 30.0 atom % or less, more preferably 15.0 atom % or more and 26 atom % or less.
- the concentration of F atoms is 8.1 atom % or more, the surface of the cured resin is excellent in liquid repellency.
- the concentration of F atoms is 30 atom % or less, aggregation of F atoms can be suppressed, and a cured resin product with few defects can be obtained.
- the concentration of Si atoms is 1.0 atom % or more and 6.0 atom % or less, more preferably 1.5 atom % or more and 4.5 atom % or less.
- the Si atom concentration is 1.0 atom % or more, the UV ozone resistance of the cured resin is improved, and good liquid repellency can be obtained even after the UV ozone treatment.
- the concentration of Si atoms is 6.0 atom % or less, aggregation of Si atoms can be suppressed, and a cured resin product with few defects can be obtained.
- a compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms for example, a compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms, and a compound having a siloxane structure
- a method of forming a resin cured product from a photosensitive resin composition containing (a-2) can be mentioned.
- a siloxane structure refers to a structure in which silicon (Si) and oxygen (O) are alternately bonded.
- It may contain two types of compounds (a-1) having a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms and a compound (a-2) having a siloxane structure, and the polysiloxane ( As in A), one compound may have a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms and a siloxane structure.
- a compound for example, a compound (a There is a method of adjusting the content of -1). Increasing the content can increase the concentration of F atoms in property (i), and decreasing the content can decrease the concentration of F atoms in property (i). There is also a method of adjusting the concentration of the fluorinated alkyl group possessed by the compound (a-1). Increasing the concentration of fluorinated alkyl groups can increase the concentration of F atoms in property (i), and decreasing the concentration of fluorinated alkyl groups can decrease the concentration of F atoms in property (i).
- a method for adjusting the Si atom concentration of the characteristic (i) to the above range for example, there is a method of adjusting the content of the compound (a-2) having a siloxane structure in the photosensitive resin composition. Increasing the content can increase the concentration of Si atoms of characteristic (i), and decreasing the content can decrease the concentration of Si atoms of characteristic (i). There is also a method of adjusting the concentration of the siloxane structure possessed by compound (a-2). Increasing the concentration of siloxane structures can increase the concentration of Si atoms in property (i), and decreasing the concentration of siloxane structures can decrease the concentration of Si atoms in property (i).
- the structure of the compound (a-1) having a fluorinated alkyl group with 7 to 21 fluorine atoms and 5 to 12 carbon atoms is not particularly limited.
- Polysiloxane (A) which will be described later, is preferable from the viewpoint of UV ozone resistance.
- the structure of compound (a-2) having a siloxane structure is not particularly limited. Examples thereof include alkyl-modified silicone, polyether-modified silicone, and polysiloxane (A) described later. Polyether-modified silicone and polysiloxane (A), which will be described later, are preferred from the viewpoint of uneven distribution on the surface of the cured resin. Furthermore, from the viewpoint of liquid repellency, polysiloxane (A), which will be described later, is more preferable.
- Products commercially available as polyether-modified silicones include, for example, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-642 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH8400, SH8700, SF8410 (manufactured by Dow Corning Toray Co., Ltd.), BYK-300, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330 (manufactured by BYK-Chemie) and the like.
- Characteristic (i) is preferably analyzed with an XPS device with a detector tilt of 45° with respect to the sample surface. Since the inclination of the detector is 45°, the area near the surface of the cured resin can be analyzed.
- Characteristic (ii) is perpendicular to the interface between the first electrode and the cured resin and in the direction from the substrate to the cured product, and has a range of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. measured by either When the thickness of the cured resin is 200 nm or less, the median thickness of the cured resin is measured. By having F atoms in the cured resin material, the water absorption of the cured resin material is lowered and the corrosion of the electrodes is suppressed, so that the durability of the display device can be improved.
- the concentration of F atoms is 0.1 atom % or more and 8.0 atom % or less, preferably 4.0 atom % or more and 7.5 atom % or less.
- the concentration of F atoms is 0.1 atom % or more, the water absorbency of the cured resin is lowered to suppress the corrosion of the electrodes, so that the durability of the display device can be improved.
- the concentration of F atoms is 8.0 atom % or less, both durability of the display device and good mechanical properties of the cured resin can be achieved.
- a method for the laminate of the present invention to satisfy the property (ii) includes, for example, a method of forming a resin cured product from a photosensitive resin composition containing an alkali-soluble resin (b-1) having a CF 3 group. . CF 3 groups are less likely to be unevenly distributed on the surface of the cured resin, and can retain F atoms inside the cured resin.
- a method for adjusting the concentration of F atoms in the characteristic (ii) to the above range for example, there is a method of adjusting the content of the alkali-soluble resin (b-1) having a CF 3 group in the photosensitive resin composition. be. Increasing the content can increase the concentration of F atoms of property (ii), and decreasing the content can decrease the concentration of F atoms of property (ii). There is also a method of adjusting the concentration of CF 3 groups possessed by the alkali-soluble resin (b-1). Increasing the concentration of CF3 groups can increase the concentration of F atoms in property (ii), and decreasing the concentration of CF3 groups can decrease the concentration of F atoms in property (ii).
- the alkali-soluble resin (b-1) having a CF 3 group is not limited in the type of main chain skeleton and side chains of the polymer constituting the resin. Examples include, but are not limited to, polyimide resins, polybenzoxazole resins, polyamideimide resins, acrylic resins, novolac resins, polyhydroxystyrene resins, phenolic resins, and polysiloxane resins. From the viewpoint of heat resistance, the alkali-soluble resin (b-1) having CF 3 groups is selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors of any of these, and copolymers thereof. It is preferable to include more than one type. Since these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgas at a high temperature of 200° C. or higher after heat treatment is reduced, and the durability of the display device can be improved.
- Characteristic (ii) excavates the cured product with Ar gas cluster ions (Ar-GCIB), is perpendicular to the interface where the first electrode and the cured product are in contact, and is in the direction from the substrate to the cured product, starting from the first electrode. It can be obtained by X-ray photoelectron spectroscopy (XPS) analysis after exposure to light anywhere in the range of 100-200 nm.
- XPS X-ray photoelectron spectroscopy
- the thickness of the cured resin starting from the interface where the first electrode and the cured resin are in contact is preferably 0.8 to 10 ⁇ m. If the thickness is 0.8 ⁇ m or more, the functional ink can be easily retained when the functional ink is applied to the region where at least a part of the cured resin on the first electrode is open. Moreover, the thickness is preferably 10 ⁇ m or less from the viewpoint of facilitating processing by photolithography or the like.
- the method of forming the cured resin material in which at least a portion of the first electrode is open there is no particular limitation on the method of forming the cured resin material in which at least a portion of the first electrode is open.
- it can be formed by using the method for producing a resin cured product of a photosensitive resin composition described below.
- a method of forming a cured resin on the front surface of the substrate masking an arbitrary region with a photoresist, and then etching the opening.
- the cured resin material included in the laminate of the present invention is not particularly limited as long as it has the above properties (i) and (ii) as determined by XPS analysis.
- a resin cured product having such characteristics can form a resin cured product satisfying both the characteristics (i) and the characteristics (ii) by using, for example, a photosensitive resin composition described below.
- a cured resin product having the property (i) and a cured resin product having the property (ii) may be laminated.
- a laminate of the present invention includes a substrate.
- the substrate metal, glass, resin film, or the like, which is preferable for supporting the display device or transporting in the post-process, can be appropriately selected. If it is a glass substrate, soda-lime glass, alkali-free glass, or the like can be used, and the thickness should be sufficient to maintain mechanical strength.
- the material of the glass it is preferable to use non-alkali glass because the fewer ions eluted from the glass, the better.
- soda-lime glass with a barrier coating such as SiO 2 is also available on the market and can be used. can.
- the resin film preferably contains a resin material selected from polyimide, polyamide, polybenzoxazole, polyamideimide, and poly(p-xylylene), and it may contain these resin materials alone, A plurality of species may be combined.
- a resin film with polyimide a solution containing polyamic acid (partially imidized polyamic acid), which is a polyimide precursor, or a solution containing soluble polyimide is applied to the supporting substrate and baked. It can also be formed by peeling off the polyimide resin film from the supporting substrate later.
- the laminate of the present invention includes a first electrode patterned on a substrate.
- the first electrode preferably contains ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), Ag, Al, or the like.
- the patterning of the first electrode can be performed by a known method. For example, there is a method of forming the first electrode on the entire surface of the substrate by a sputtering method, then masking an arbitrary region with a photoresist, and then etching the opening.
- a planarizing layer may be further laminated between the substrate and the first electrode patterned on the substrate.
- TFTs thin film transistors
- wirings located on the sides of the TFTs and connected to the TFTs are often provided on a substrate such as glass. If the first electrode follows the unevenness of the wiring, an appearance defect such as uneven light emission occurs. Therefore, a planarization layer is formed on the drive circuit so as to cover the unevenness, and a first electrode is provided on the planarization layer.
- the planarizing layer preferably contains a resin material selected from polyimide, polyamide, polybenzoxazole, polyamideimide, acrylic, cardo, and poly(p-xylylene), and contains these resin materials alone. may be used, or a combination of multiple types may be used.
- FIG. 4 shows a schematic cross-sectional view of an example of the laminate of the present invention.
- a flattening layer 14, a patterned first electrode 8, and a cured resin material 16 are laminated in this order on a substrate 13, and at least a part of the cured resin material 16 on the patterned first electrode 8 is opened.
- the characteristic (i) of the cured resin by X-ray photoelectron spectroscopy (XPS) is measured from the surface 17 opposite to the interface where the first electrode and the cured resin are in contact.
- XPS is preferably measured within a range of 100 ⁇ m from the edge of the opening of the cured resin 16 .
- the characteristic (ii) is perpendicular to the interface 18 where the first electrode and the cured resin are in contact, and in the direction from the substrate to the cured resin, starting from the interface where the first electrode and the cured resin are in contact. from 100 nm to 30 nm, that is, perpendicular to the interface between the first electrode and the cured resin, and in the direction from the substrate to the cured resin, and 100 nm from the interface between the first electrode and the cured resin. Measured anywhere in the range 19 from ⁇ 200 nm. In the opening of the first electrode patterned on the substrate, the first electrode and the cured resin are perpendicular to the interface between the first electrode and the cured resin and in the direction from the substrate to the cured resin.
- the first electrode Assuming that the first electrode is present, measurement is performed in any range of 100 to 200 nm from the height of the first electrode, as shown in the range 19 of 100 to 200 nm from the interface of . In addition, when the thickness of the first electrode varies, it is assumed that the first electrode having the average thickness of the edge of the opening is present in the opening of the patterned first electrode.
- the laminate of the present invention has C1s spectrum [A] of the cured resin material measured from at least a part of the surface of the cured resin material opposite to the interface where the first electrode and the cured resin material are in contact; It is perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction of the cured resin from the substrate, and within a range of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact.
- the C1s spectrum [B] of the cured resin to be measured is It is preferable to satisfy properties (iii) and (iv).
- the peak height in C1s spectrum [A] is higher than the peak height of the peak derived from CF 2 group having a peak top within the binding energy range of 290 to 292 eV in C1s spectrum [B].
- the height of the peak derived from the CF 3 group having a peak top within the range of 292 to 294 eV in the C1s spectrum [A] is higher in the C1s spectrum [B].
- the C1s spectrum [A] is the spectrum of the surface of the cured resin measured from at least part of the surface of the cured resin on the opposite side of the interface between the first electrode and the cured product.
- the C1s spectrum [B] is perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction of the cured resin from the substrate. It is the spectrum inside the cured product measured in one of the ranges. When the thickness of the cured resin is 200 nm or less, the median thickness of the cured resin is measured.
- the surface of the cured resin material is excellent in liquid repellency.
- Structures showing peaks derived from CF2 groups with peak tops in the range of 290 to 292 eV in binding energies include, for example, heptafluoropentyl group, nonafluorohexyl group, tridecafluorooctyl group, heptadecafluorodecyl group, 5 ,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl groups, etc., and have the property of being unevenly distributed on the surface of the cured resin, and are good for the surface of the cured resin.
- liquid repellency can be imparted.
- the cured resin material included in the laminate of the present invention exhibits the property (iv), the water absorption of the cured resin material is reduced and the corrosion of the electrodes is suppressed, so that the durability of the display device can be improved.
- CF 3 groups are less likely to be unevenly distributed on the surface of the cured resin, and can retain F atoms inside the cured resin.
- the characteristics (iii) and (iv) are preferably obtained by comparing C1s spectra [A] and C1s spectra [B] measured with the same XPS device.
- a C1s spectrum [A] is measured from at least part of the surface of the cured resin on the side opposite to the interface where the first electrode and the cured resin are in contact. Subsequently, the cured resin material was excavated by Ar gas cluster ions (Ar-GCIB), perpendicular to the interface between the first electrode and the cured resin material, and in the direction from the substrate to the cured material.
- the C1s spectrum [B] can be measured after exposing any of the range of 100 to 200 nm starting from the interface of the cured product.
- FIG. 4 shows a schematic cross-sectional view of an example of the laminate of the present invention.
- a flattening layer 14, a patterned first electrode 8, and a cured resin 16 are laminated in this order on a substrate 13, and at least a portion of the cured resin 16 on the first electrode 8 is open.
- the C1s spectrum [A] is measured from the surface 17 opposite to the interface where the first electrode and the cured resin are in contact. It is preferable to measure within a range of 100 ⁇ m from the edge of the opening of the cured resin 16 .
- the C1s spectrum [B] is perpendicular to the interface 18 where the first electrode and the cured resin are in contact, and is in the direction of the cured resin from the substrate, and the interface where the first electrode and the cured resin are in contact is A range of 100 nm30 to 100 nm from the starting point, that is, perpendicular to the interface between the first electrode and the cured resin material, and in the direction from the substrate to the cured resin material, starting from the interface between the first electrode and the cured resin material It is measured anywhere in the range 19 from 100 to 200 nm.
- the interface between the first electrode and the cured resin is perpendicular to the interface between the first electrode and the cured resin and in the direction from the substrate to the cured resin.
- the first electrode is present, it is measured either in the range 19 from 100 to 200 nm from the height of the first electrode, as in the range 19 from 100 to 200 nm.
- the thickness of the first electrode varies, it is assumed that the first electrode having the average thickness of the edge of the opening is present in the opening of the patterned first electrode.
- a cured resin material that satisfies the properties (i) to (iv) is formed. can do.
- a cured resin product having the properties (i) and (iii) and a cured resin product having the properties (ii) and (iv) may be laminated to form.
- the cured resin preferably contains a compound having an imide ring structure.
- a compound having an imide ring structure is preferably a structure derived from a polyimide resin or a residue thereof.
- polyimide resins include polyimides, polyamideimides, precursors thereof, and copolymers thereof described in the alkali-soluble resin (B) described later. Since the resin cured product contains a compound having an imide ring structure, the amount of outgas at high temperatures is small, and when the laminate is used in an organic EL display device, the pixel shrinkage is small and the organic EL display device is excellent in durability. Obtainable.
- the cured resin preferably contains a compound having an indene structure.
- the compound having an indene structure is preferably a structure derived from a quinonediazide compound or a residue thereof.
- the quinonediazide compound include the quinonediazide compound (C-2) described later.
- a positive-type photosensitive resin composition can be obtained by including a quinonediazide compound in the photosensitive resin composition described below.
- the cured resin product when the cured resin product is a cured product of a positive-type photosensitive resin composition, the surface of the cured resin product formed by "half exposure" described later has no liquid repellency, and a good ink can be obtained. It can have coatability. That is, a cured resin product with a liquid-repellent surface and a cured resin product with a lyophilic surface can be formed by a single photolithography.
- the cured resin material has a thickness of 0.8 ⁇ m to 10.0 ⁇ m starting from the interface of the first electrode and the cured resin material, and the first electrode and the cured resin material A step-shaped cured resin having a second step with a thickness of 0.1 ⁇ m to 0.7 ⁇ m starting from the interface of the It is preferable that the first stage of the cured resin satisfies the property (i) and the second stage of the cured resin satisfies the property (v).
- the first stage having a thickness of 0.8 ⁇ m to 10.0 ⁇ m starting from the interface between the first electrode and the cured resin is a cured resin having the property (i) and having a liquid-repellent surface. If the thickness is 0.8 ⁇ m or more, the functional ink can be easily retained when the functional ink is applied to the region where at least a part of the cured resin on the first electrode is open. Moreover, the thickness is preferably 10.0 ⁇ m or less from the viewpoint of facilitating processing by photolithography or the like.
- the second stage which has a thickness of 0.1 ⁇ m to 0.7 ⁇ m starting from the interface between the first electrode and the cured resin, is a cured resin with a hydrophilic surface having the characteristic (v).
- the characteristic (v) is the characteristic of the surface of the cured resin measured from at least part of the surface opposite to the interface between the first electrode and the cured resin in the second stage of the cured resin.
- the functional ink is continuously inkjetted from the area where at least a part of the cured resin on the first electrode is open to the second stage of the cured resin.
- the functional layer is formed by coating, it is possible to suppress defects such as white spots in the functional layer.
- the concentration of F atoms measured from at least a part of the surface of the cured resin material on the opposite side of the interface between the first electrode and the cured resin material is 0.1 atom % or more and 20.0 atom %. or less, preferably 8.0 atom % or more and 18.0 atom % or less.
- the F atom concentration is 0.1 atom % or more, the water absorption of the cured resin is low, and the durability when used in a display device can be improved.
- the concentration of F atoms is 20.0 atom %, aggregation of F atoms can be suppressed.
- the characteristic (v) is the maximum peak height measured in the range of binding energy 290 to 295 eV in the C1s spectrum measured from at least a part of the surface opposite to the interface where the first electrode and the cured resin are in contact.
- the peaks with are derived from CF 3 groups with peak tops in the range of 292-294 eV.
- the fluorine structure is CF 3 groups, both the lyophilicity of the cured resin surface and the durability of the display device can be achieved.
- the concentration of Si atoms measured from the surface of the cured resin material opposite to the interface where the first electrode and the cured resin material are in contact is 0.1 atom% or more and 0.9 atom% or less; More preferably, it is 0.1 atom % or more and 0.5 atom % or less.
- the Si atom concentration is 0.1 atom % or more, the adhesiveness to the electrode is improved, and the durability of the display device can be improved.
- the concentration of Si atoms is 0.9 atom % or less, the cured resin surface can exhibit good lyophilicity.
- the characteristic (i) is preferably measured within a range of 100 ⁇ m from the edge of the first stage opening of the cured resin. By measuring this range, it is possible to analyze the liquid repellency of the surface of the first stage cured resin to the functional ink. Also, the characteristic (v) is preferably measured within a range of 100 ⁇ m from the end of the second stage opening of the cured resin. By measuring this range, it is possible to analyze the hydrophilicity of the surface of the cured resin second stage with respect to the functional ink.
- a photosensitive resin containing an alkali-soluble resin (b-1) having a CF 3 group and an alkali-soluble resin (b-2) having a siloxane structure A method of forming a resin cured product from the composition may be mentioned.
- the alkali-soluble resin (b-1) having a CF 3 group may have a siloxane structure.
- a method for adjusting the concentration of the F atom of the characteristic (v) within the above range for example, there is a method of adjusting the content of the alkali-soluble resin (b-1) having a CF 3 group in the photosensitive resin composition. be. Increasing the content can increase the concentration of F atoms of property (v), and decreasing the content can decrease the concentration of F atoms of property (v). There is also a method of adjusting the concentration of CF 3 groups possessed by the alkali-soluble resin (b-1). Increasing the concentration of CF3 groups can increase the concentration of F atoms in characteristic (v), and decreasing the concentration of CF3 groups can decrease the concentration of F atoms in characteristic (v).
- the Si atom concentration of the characteristic (v) to the above range
- Increasing the content can increase the concentration of Si atoms of characteristic (v)
- decreasing the content can decrease the concentration of Si atoms of characteristic (v).
- Increasing the concentration of siloxane structures can increase the concentration of Si atoms in property (v)
- decreasing the concentration of siloxane structures can decrease the concentration of Si atoms in property (v).
- Characteristic (v) is preferably analyzed with an XPS device with a detector tilt of 45° with respect to the sample surface. Since the inclination of the detector is 45°, the area near the surface of the cured resin can be analyzed.
- a laminate comprising a step-shaped cured resin material having the first stage and the second stage is formed from a cured resin material having at least the property (i), the property (ii), and the property (v), for example. can do.
- a laminate can be formed, for example, by using the photosensitive resin composition described below. Specifically, when a positive photosensitive resin composition is used, the first stage having the characteristic (i) is formed in the unexposed area, and the second stage having the characteristic (v) is formed by the "half-exposed area" described later. Two stages can be formed, and the inside of the cured resin can exhibit the characteristic (ii). Alternatively, a cured resin product having the property (i) and a cured resin product having the property (v) may be laminated. When laminating two types of resin cured products, at least one type of resin cured product has the property (ii). From the viewpoint of the durability of the display device, it is more preferable that the two types of resin cured products have the property (ii).
- a laminate comprising a step-shaped cured resin material having the first step and the second step, for example, a first electrode 8 patterned on a substrate as shown in FIG. 2 or 3,
- a laminate consisting of a first stage 9, which is laminated in order of the cured resin material and defines an area where the cured resin material is inkjet-coated, and a second stage 10, which defines two or more areas arranged in the area.
- a functional layer 11 continuously arranged on the first electrode 8 patterned on the substrate and the second stage 10 of the cured resin can be formed by an inkjet coating method.
- a laminate comprising step-shaped cured resin products having the first step and the second step can be formed by using a photosensitive resin composition.
- a photosensitive resin dried product obtained from a positive photosensitive resin composition is prepared, and in the subsequent exposure step, the unexposed area, half exposure A part and an exposure part are formed.
- a developing process and a heat treatment process are performed, a first stage 9 of the cured resin material can be formed in the unexposed area, and a second stage 10 of the cured resin material can be formed in the half-exposed area, and the exposed area can be patterned on the substrate.
- the exposed first electrode 8 is exposed.
- a second stage 10 of the cured resin and a first stage 9 of the cured resin may be laminated in this order on the first electrode 8 patterned on the substrate.
- FIG. 5 shows a schematic cross-sectional view of another example of the laminate of the present invention.
- the planarizing layer 14, the patterned first electrode 8, and the cured resin are laminated in this order on the substrate 13, and the cured resin has an opening at least partly on the first electrode 8, and the cured resin It has a first stage 9 and a second stage 10 of cured resin.
- Characteristic (i) of the cured resin by X-ray photoelectron spectroscopy (XPS) analysis is measured from the surface 20 opposite to the interface where the first electrode of the first step of the cured resin and the cured resin come into contact.
- the characteristic (v) is measured from the surface 21 opposite to the interface where the first electrode of the second stage of the cured resin and the cured resin are in contact.
- XPS X-ray photoelectron spectroscopy
- Characteristic (ii) is perpendicular to the interface 18 where the first electrode and the cured resin are in contact, and is in the direction from the substrate to the cured resin.
- the interface between the first electrode and the cured resin is perpendicular to the interface between the first electrode and the cured resin and is in the direction of the cured resin from the substrate.
- the first electrode Assuming that the first electrode is present, it is measured either in the range 19 from 100 to 200 nm from the height of the first electrode, as in the range 19 from 100 to 200 nm. In addition, when the thickness of the first electrode varies, it is assumed that the first electrode having the average thickness of the edge of the opening is present in the opening of the patterned first electrode. Subsequently, the functional layer 11 continuously arranged on the first electrode 8 patterned on the substrate and the second stage 10 of the cured resin can be formed by an inkjet coating method.
- the cured resin is not particularly limited as long as it has the properties described above.
- a method for forming a cured resin material satisfying properties (i) to (v) for example, a compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms, a siloxane structure, a compound (a- 2 ) having a CF group, an alkali-soluble resin (b-1) having a CF group and a photosensitive resin composition containing an alkali-soluble resin (b-2) having a siloxane structure to form a cured resin product. mentioned.
- preferred structures of the alkali-soluble resin (b-1) having a CF 3 group and the alkali-soluble resin (b-2) having a siloxane structure include the alkali-soluble resin (B) described later. mentioned.
- the polysiloxane (A) will be explained.
- polysiloxane (A) By including polysiloxane (A) in the photosensitive resin composition, it is possible to impart high liquid repellency to the upper surface of the cured resin. Furthermore, the polysiloxane of the main chain has high UV ozone resistance, and can easily impart high liquid repellency to the upper surface of the resin cured product after UV ozone treatment.
- the polysiloxane (A) has a repeating unit structure represented by formula (1) and/or a repeating unit structure represented by formula (2).
- R f in the repeating unit structure represented by formula (1) and/or the repeating unit structure represented by formula (2) is a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms. More preferably, it is a fluorinated alkyl group having 9 to 13 fluorine atoms and 6 to 8 carbon atoms.
- a fluorinated alkyl group having 7 or more fluorine atoms and 5 or more carbon atoms makes it easier for the cured resin product to satisfy the property (i), and the upper surface of the cured resin product can exhibit better liquid repellency.
- the fluorinated alkyl group of R f has a CF 2 group.
- the alkyl fluoride group has a CF 2 group
- the cured resin product easily satisfies the property (iii), and the upper surface of the cured resin product can exhibit better liquid repellency.
- fluorinated alkyl groups having a CF2 group include heptafluoropentyl, nonafluorohexyl, tridecafluorooctyl, heptadecafluorodecyl, 5,5,6,6,7,7,7 -heptafluoro-4,4-bis(trifluoromethyl)heptyl group and the like.
- Nonafluorohexyl groups and tridecafluorooctyl groups having 9 to 13 fluorine atoms and 6 to 8 carbon atoms are preferred from the viewpoint of liquid repellency and environmental load.
- Polysiloxane (A) has a total repeating unit structure represented by formula (1) and a repeating unit structure represented by formula (2) in 100 mol% of the total repeating unit structure of polysiloxane (A). It is preferable to include mol %. More preferably, it is 10 to 25 mol %. By containing 5 mol% or more of the repeating unit structure represented by formula (1) and/or the structure represented by formula (2), the cured resin product easily satisfies the property (i), and exhibits better liquid repellency. can be shown. Moreover, aggregation of the fluorinated alkyl group can be reduced by setting the amount to 30 mol % or less.
- polysiloxane (A) preferably has a repeating unit structure of (I) and (II).
- (I) a repeating unit structure represented by formula (3) and/or a repeating unit structure represented by formula (4)
- R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms.
- R 2 is an aryl group having 6 to 15 carbon atoms,
- R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms, and
- Y is 1 or 2.
- R 4 is an organic group having 2 to 20 carbon atoms containing an acidic group. * indicates a covalent bond.
- Polysiloxane (A) preferably has (I) a repeating unit structure represented by formula (3) and/or a repeating unit structure represented by formula (4). Since the repeating unit structure represented by the formula (3) and/or the repeating unit structure represented by the formula (4) has an aryl group, the steric hindrance of the aryl group suppresses the aggregation of the fluorinated alkyl group described above, and the defect It becomes easy to obtain a cured product with less
- R 2 is an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, 4-methyl Phenyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 4-t-butylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-phenylethyl group, 4-hydroxybenzyl group, and formula (7 ) and the like.
- * indicates a covalent bond directly connected to R3.
- R3 is a single bond , it represents a covalent bond directly connected to a silicon atom.
- a is an integer from 1 to 3; From the viewpoint of chemical resistance, a is preferably 1 to 2, more preferably 1. Specific examples of these are represented by general formulas, and the following structures are given.
- R 2 has the effect of suppressing the aggregation of the fluorinated alkyl group and from the viewpoint of controlling the polymerizability.
- R 2 has the effect of suppressing the aggregation of the fluorinated alkyl group and from the viewpoint of controlling the polymerizability.
- Y in the repeating unit structure represented by formula (4) is more preferably 1.
- R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Specific examples of are a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, t-butylene group and the like.
- the total repeating unit structure represented by formula (3) and the repeating unit structure represented by formula (4) is included in 20 to 70 mol% in 100 mol% of the total repeating unit structure of polysiloxane (A). More preferably, it is 30 to 60 mol %.
- the total amount of the repeating unit structure represented by the formula (3) and the repeating unit structure represented by the formula (4) is 20 mol% or more, a favorable effect of suppressing aggregation of the fluorinated alkyl group is likely to be exhibited. From the viewpoint of polymerizability control, it is preferably 70 mol % or less.
- Polysiloxane (A) has (II) a repeating unit structure represented by formula (5) and/or a repeating unit structure represented by formula (6). Since the repeating unit structure represented by formula (5) and/or the repeating unit structure represented by formula (6) has an organic group having 2 to 20 carbon atoms including an acidic group, the solubility in an alkaline developer is improved. It becomes easy to clean, and the residue in the opening can be reduced. Moreover, it becomes easy to suppress aggregation of the above-mentioned fluorinated alkyl group, and it becomes easy to obtain a hardened
- the organic group having 2 to 20 carbon atoms containing an acidic group is an organic group having 2 to 20 carbon atoms containing at least one acidic group selected from the group consisting of a carboxyl group, a carboxylic anhydride group, a hydroxyl group and a sulfonic acid group. is preferred, and more preferred is a structure represented by formula (8) or formula (9).
- R 15 is a single bond or an alkylene group having 1 to 10 carbon atoms. * indicates a covalent bond.
- R 4 more preferably has a carboxyl group. Furthermore, it is more preferably a dicarboxy group obtained by hydrolyzing a carboxylic anhydride group.
- organic groups having 2 to 20 carbon atoms containing an acidic group include 2-hydroxyethyl group, 3-hydroxypropyl group, bis(2-hydroxyethyl)-3-aminopropyl group, carboxymethyl group, 2- Examples include a carboxyethyl group, a 3-carboxypropyl group, and structures ( ⁇ ) and structures ( ⁇ ) shown below.
- As the structure having a carboxyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, structure ( ⁇ ), and structure ( ⁇ ) are preferable, and structure ( ⁇ ) and structure ( ⁇ ) are more preferable.
- * indicates a covalent bond directly connected to the silicon atom.
- a total of 1 to 40 mol% of the repeating unit structure represented by formula (5) and the repeating unit structure represented by formula (6) is contained in 100 mol% of the total repeating unit structure of polysiloxane (A). More preferably, it is 5 to 30 mol %.
- the total content of the repeating unit structure represented by formula (5) and the repeating unit structure represented by formula (6) is 1 mol % or more, better ink wettability and compatibility can be exhibited at the opening. Further, when the content is 40 mol % or less, better liquid repellency can be obtained.
- the polysiloxane (A) may have (III) a repeating unit structure represented by formula (10) and/or a repeating unit structure represented by formula (11).
- R 1 hydrogen atom, C 1-6 alkyl group, C 1-6 acyl group or C 6-15 aryl group
- R 5 is other than R f
- R 2 -R 3 - and R 4 represents an organic group having 1 to 10 carbon atoms.
- R 5 is not particularly limited as long as it is an organic group having 1 to 10 carbon atoms other than R f , R 2 -R 3 - and R 4 .
- R 5 include hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclohexyl group; Amino group-containing groups such as propyl group, N-(2-aminoethyl)-3-aminopropyl group, N- ⁇ -(aminoethyl)- ⁇ -aminopropyl group; Cyano group-containing groups such as ⁇ -cyanoethyl group ; glycidoxymethyl group, ⁇ -glycidoxyethyl group, ⁇ -glycidoxypropyl group, ⁇ -glycidoxypropyl group, ⁇ -glycidoxy
- R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms.
- a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are preferable.
- Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and the like.
- a hydrogen atom, a methyl group, and an ethyl group are more preferable from the viewpoint of polymerizability control.
- the content of polysiloxane (A) is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (B). More preferably, it is 0.2 parts by mass or more and 5 parts by mass or less.
- the content of the polysiloxane (A) is 0.1 parts by mass or more, the cured resin product easily satisfies the property (i), and better liquid repellency is easily obtained.
- the content is 10 parts by mass or less, it becomes easier to suppress the above-mentioned aggregation of the fluorinated alkyl groups.
- Polysiloxane can be obtained by hydrolyzing and polycondensing alkoxysilanes represented by the following general formulas (12), (13), (14) and (15) in a solvent.
- (A) Polysiloxane is preferably the polysiloxane thus obtained.
- R f is a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms
- R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or 6 to 15 carbon atoms is an aryl group of
- R 2 is an aryl group having 6 to 15 carbon atoms
- R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms
- Y is 1 or 2.
- R 4 is an organic group having 2 to 20 carbon atoms containing an acidic group.
- R 5 is an organic group having 1 to 10 carbon atoms.
- the hydrolysis reaction is carried out by adding an acid catalyst and water to the alkoxysilanes represented by the general formulas (12), (13), (14) and (15) in a solvent at room temperature to 110° C. for 1 to 180 minutes. It is preferable to react. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed.
- the reaction temperature is more preferably 40-105°C.
- the reaction solution After obtaining the silanol compound by the hydrolysis reaction, it is preferable to heat the reaction solution at 50° C. or higher and the boiling point of the solvent or lower for 1 to 100 hours to carry out the condensation reaction. Moreover, in order to increase the degree of polymerization of the siloxane compound obtained by the condensation reaction, it is possible to add an acid or base catalyst or to reheat.
- Various conditions in the hydrolysis reaction can be appropriately set in consideration of the reaction scale, the size and shape of the reaction vessel, etc. For example, by setting the acid concentration, reaction temperature, reaction time, etc., a polysiloxane having a desired degree of polymerization can be obtained.
- Ion-exchanged water is preferable as the water used for the hydrolysis reaction.
- the amount of water can be selected arbitrarily, it is preferably used in the range of 1.0 to 4.0 mol per 1 mol of the alkoxysilane compound.
- Solvents used for the hydrolysis reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, benzyl alcohol, 2-methylbenzyl
- Acid catalysts used for the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acids or their anhydrides, and ion exchange resins. Acidic aqueous solutions using formic acid, acetic acid or phosphoric acid are particularly preferred.
- a preferable content of the acid catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of all the alkoxysilane compounds used during the hydrolysis reaction. Also, the content of the acid catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
- the total amount of alkoxysilane compound means the amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.
- the polysiloxane solution after hydrolysis and partial condensation does not contain the above catalyst, and the catalyst can be removed as necessary.
- washing with water and/or treatment with an ion exchange resin are preferred from the standpoint of ease of operation and removability. Washing with water is a method of diluting a polysiloxane solution with a suitable hydrophobic solvent, washing with water several times, and concentrating the obtained organic layer with an evaporator or the like.
- Ion exchange resin treatment is a method of contacting a polysiloxane solution with a suitable ion exchange resin.
- the weight average molecular weight (Mw) of (A) polysiloxane is not particularly limited, but is preferably 500 or more, more preferably 1,500 or more in terms of polystyrene measured by gel per emission chromatography (GPC). Also, it is preferably 20,000 or less, more preferably 10,000 or less.
- the alkali-soluble resin in the present invention refers to a resin having a dissolution rate of 50 nm/min or higher as defined below. More specifically, a silicon wafer is coated with a solution of a resin dissolved in ⁇ -butyrolactone and prebaked at 120° C. for 4 minutes to form a prebaked film with a thickness of 10 ⁇ m ⁇ 0.5 ⁇ m. A resin having a dissolution rate of 50 nm/min or more, which is obtained from the reduction in thickness when immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 1°C for 1 minute and then rinsed with pure water. .
- TMAH tetramethylammonium hydroxide
- the alkali-soluble resin (B) preferably has an alkali-soluble group in the structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility.
- An alkali-soluble group refers to a functional group that interacts or reacts with an alkali to increase the solubility in an alkali solution.
- Preferred alkali-soluble groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups.
- the alkali-soluble resin (B) has a structure having the aforementioned alkali-soluble group
- the main chain skeleton of the polymer constituting the resin and the types of side chains are not limited. Examples include, but are not limited to, polyimide resins, polybenzoxazole resins, polyamideimide resins, acrylic resins, novolac resins, polyhydroxystyrene resins, phenolic resins, and polysiloxane resins.
- the alkali-soluble resin (B) preferably has a CF 3 group. Having 3 CF groups makes it easier for the cured resin to satisfy the characteristics (ii) and (iv), and the water absorption of the cured resin is reduced to suppress corrosion of the electrodes, thereby improving the durability of the display device. can be improved. CF 3 groups are less likely to be unevenly distributed on the surface of the cured resin, and can retain F atoms inside the cured resin. In addition, having a CF3 group contributes to the concentration of F atoms in the property (v) of the cured resin and the C1s spectrum. Since three CF groups do not exhibit liquid repellency, it is possible to easily achieve both the lyophilicity of the cured resin surface and the durability of the display device.
- the alkali-soluble resin (B) preferably has a siloxane structure. Having a siloxane structure contributes to the concentration of Si atoms in the characteristic (v) of the cured resin. Moreover, the adhesiveness to the electrode is improved, and the durability of the display device can be further improved.
- the alkali-soluble resin (B) contained in the photosensitive resin composition preferably has an imide ring structure. It is more preferable to contain one or more selected from the group consisting of polyimide, polyamideimide, precursors thereof and copolymers thereof. These alkali-soluble resins may be used alone, or a plurality of alkali-soluble resins may be used in combination.
- an imide ring structure By having an imide ring structure, the amount of outgassing at high temperatures is small, and when the laminate is used in an organic EL display device, pixel shrinkage is small, and an organic EL display device with more excellent durability can be obtained.
- polybenzoxazole and/or its precursor may be contained as a highly heat-resistant resin.
- a polyimide can be obtained, for example, by reacting a tetracarboxylic acid, a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride, or the like with a diamine or a diisocyanate compound, a trimethylsilylated diamine, or the like.
- Polyimide has a tetracarboxylic acid residue and a diamine residue.
- Polyimide can be obtained, for example, by subjecting polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, to dehydration ring closure by heat treatment.
- a water-azeotropic solvent such as m-xylene may be added.
- a dehydration condensing agent such as carboxylic anhydride or dicyclohexylcarbodiimide or a base such as triethylamine may be added as a ring-closing catalyst, and dehydration and ring-closure may be effected by chemical heat treatment.
- it can be obtained by adding a weakly acidic carboxylic acid compound and subjecting it to heat treatment at a low temperature of 100° C. or lower for dehydration and ring closure.
- Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol compound with a dicarboxylic acid, a dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like. Polybenzoxazole has dicarboxylic acid residues and bisaminophenol residues. Further, polybenzoxazole can be obtained, for example, by dehydrating and ring-closing polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound and a dicarboxylic acid, by heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc., followed by dehydration and ring closure by chemical treatment.
- polyimide precursors examples include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.
- polyamic acid can be obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, or the like with diamine, diisocyanate compound, or trimethylsilylated diamine.
- Polyimide can be obtained, for example, by subjecting the polyamic acid obtained by the above method to dehydration and ring closure by heating or chemical treatment with an acid or base.
- polybenzoxazole precursors include polyhydroxyamides.
- polyhydroxyamide can be obtained by reacting bisaminophenol with dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, or the like.
- Polybenzoxazole can be obtained, for example, by subjecting the polyhydroxyamide obtained by the above method to dehydration and ring closure by heating or chemical treatment with phosphoric anhydride, a base, a carbodiimide compound, or the like.
- a polyamideimide precursor can be obtained, for example, by reacting a tricarboxylic acid, a corresponding tricarboxylic acid anhydride, or a tricarboxylic acid anhydride halide with a diamine or diisocyanate.
- Polyamideimide can be obtained, for example, by subjecting the precursor obtained by the above method to dehydration and ring closure by heating or chemical treatment with an acid or base.
- Polyimide, polybenzoxazole, polyamideimide, or a copolymer of any of these precursors may be block copolymerization, random copolymerization, alternating copolymerization, or graft copolymerization, or a combination thereof.
- a block copolymer can be obtained by reacting polyhydroxyamide with a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride, or the like. Further, dehydration and ring closure can be performed by heating or chemical treatment with an acid or base.
- Polyimides, polybenzoxazoles or polyamideimides, precursors of any of these and copolymers thereof preferably have CF 3 groups on the residues of the carboxylic acid component and/or the residues of the diamine component and have the formula (16 ) is more preferred. Since the structure represented by the formula (16) has excellent compatibility with the polysiloxane (A) described above, it is possible to suppress aggregation of the polysiloxane (A) and obtain a cured product with few defects. Furthermore, the three CF 3 groups in the structure represented by (16) lower the water absorbency of the cured product of the photosensitive resin composition, and can further improve the durability of the display device. In addition, since CF 3 groups do not impart liquid repellency, a cured product having a lyophilic surface can be formed by "half exposure" described later.
- polyimide, polybenzoxazole or polyamideimide From the viewpoint of compatibility with the above-mentioned polysiloxane (A) and water absorption of the cured resin, polyimide, polybenzoxazole or polyamideimide, precursors of any of these and copolymers thereof have a carboxylic acid component. More preferably, the residue and the residue of the diamine component have a structure represented by formula (16).
- the alkali-soluble resin (B) preferably has a structural unit represented by any one of formulas (17) to (20), and more preferably has a structural unit represented by formula (20). Two or more kinds of resins having these structural units may be contained, or two or more kinds of structural units may be copolymerized.
- the resin of the alkali-soluble resin (B) preferably contains 3 to 1000, more preferably 20 to 200, structural units represented by any one of formulas (17) to (20) in the molecule.
- R 6 and R 9 are tetravalent organic groups
- R 7 , R 8 and R 11 are divalent organic groups
- R 10 is trivalent organic groups
- R 12 is 2 to a hexavalent organic group
- R 13 represents a divalent to 12-valent organic group.
- R 14 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- p is an integer of 0-2;
- q is an integer of 0-10;
- n represents an integer of 0 to 2;
- All of R 6 to R 13 preferably have an aromatic ring and/or an aliphatic ring.
- Partial structures containing R 6 , R 8 , R 10 and R 12 (COOR 14 ) n (OH) p in formulas (17) to (20) are obtained, for example, by using corresponding carboxylic acid components. be able to. That is, for example, it can be obtained by using a tetracarboxylic acid for R6 , a dicarboxylic acid for R8 , a tricarboxylic acid for R10, and a di-, tri- or tetra - carboxylic acid for R12 .
- Examples of carboxylic acid components used to obtain R 6 , R 8 , R 10 , R 12 (COOR 14 ) n (OH) p include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, Bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, etc.
- Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenylether tricarboxylic acid, biphenyltricarboxylic acid, etc.
- tetracarboxylic acids as pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 2,2′,3,3′-biphenyltetracarboxylic acid , 3,3′,4,4′-benzophenonetetracarboxylic acid, 2,2′,3,3′-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2 , 2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis (3,4-dicarboxyphenyphenyl)methane, bis(2,3-dicarboxyphenyl)methane
- Examples include aromatic tetracarboxylic acids and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.
- aromatic tetracarboxylic acids and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.
- one or two carboxyl groups of each of tricarboxylic acid and tetracarboxylic acid correspond to COOR 14 groups.
- These acid components can be used as they are or as acid anhydrides, active esters, and the like. Also, two or more of these acid components may be used in combination.
- the alkali-soluble resin (B) preferably has a structure represented by formula (16) in the residue of the carboxylic acid component.
- the carboxylic acid component include bis(carboxyphenyl)hexafluoropropane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane and 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane are preferred.
- the partial structures containing R 7 , R 9 , R 11 and R 13 (OH) q in formulas (17) to (20) can be obtained, for example, by using corresponding diamine components.
- diamine components used to provide R 7 , R 9 , R 11 , R 13 (OH) q include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4 -hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino -4-hydroxy)biphenyl, hydroxyl group-containing diamines such as bis(3-amino-4-hydroxyphenyl)fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether, dim
- diamines can be used as they are or as corresponding diisocyanate compounds, trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components. In applications where heat resistance is required, it is preferable to use the aromatic diamine in an amount of 50 mol % or more of the total diamine.
- the alkali-soluble resin (B) preferably has a structure represented by formula (16) in the residue of the diamine component. Hexafluoropropane is preferred.
- the alkali-soluble resin (B) preferably has a siloxane-based diamine such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane as a diamine component from the viewpoint of adhesion to the electrode. It contributes to the concentration of Si atoms in the property (v) of the cured resin.
- a siloxane-based diamine such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane
- R 6 to R 13 of formulas (17) to (20) can contain phenolic hydroxyl groups, sulfonic acid groups, thiol groups, etc. in their skeletons.
- a resin having an appropriate amount of phenolic hydroxyl groups, sulfonic acid groups, or thiol groups a positive photosensitive resin composition having appropriate alkali solubility can be obtained.
- the resin of the alkali-soluble resin (B) has a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound at the main chain end. It is preferable to block with a terminal blocking agent such as.
- the introduction ratio of the monoamine used as the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50 mol%, based on the total amine component. mol% or less.
- the proportion of acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as a terminal blocker is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. above, preferably 100 mol % or less, particularly preferably 90 mol % or less.
- a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
- the repeating number of the structural unit is preferably 3 or more and 200 or less. Further, in the resin having the structural unit represented by formula (20), the repeating number of the structural unit is preferably 10 or more and 1000 or less. Within this range, a thick resin cured product can be easily formed.
- Alkali-soluble resin (B) may be composed only of structural units represented by any one of formulas (17) to (20), or may be a copolymer or mixture with other structural units. may At that time, the structural unit represented by any one of formulas (17) to (20) is preferably contained in the total resin in an amount of 10% by mass or more, more preferably 30% by mass or more. The type and amount of structural units used for copolymerization or mixing can be selected within a range that does not impair the mechanical properties of the resin cured product obtained by the final heat treatment.
- the photosensitive resin composition preferably contains a photosensitizer (C).
- a photosensitizer C
- the opening of the cured resin material on the first electrode in the laminate of the present invention can be formed by photolithography.
- the photosensitive agent (C) may be either a negative type that is cured by light or a positive type that is solubilized by light.
- a polymerizable unsaturated compound and a photopolymerization initiator (C-1), or a quinonediazide compound (C-2) can be preferably contained.
- the polymerizable unsaturated compound and the photopolymerization initiator (C-1) may be simply referred to as (C-1).
- the photosensitive agent (C) preferably contains a quinonediazide compound.
- Examples of the polymerizable unsaturated compound in (C-1) include unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group and methacryloyl group and/or unsaturated triple bond functional groups such as propargyl group.
- unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group and methacryloyl group and/or unsaturated triple bond functional groups such as propargyl group.
- conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred from the standpoint of polymerizability.
- the number of functional groups contained is preferably 1 to 4 from the standpoint of stability, and the groups do not have to be the same.
- the compound referred to here preferably has a molecular weight of 30 to 800. If the molecular weight is in the range of 30-800, the compatibility with the polymer and the reactive diluent is good.
- the content of the polymerizable unsaturated compound in (C-1) is not particularly limited, but it is preferably 5 parts by mass or more from the viewpoint of improving alkali solubility with respect to 100 parts by mass of the alkali-soluble resin (B). , 50 parts by mass or less is preferable from the viewpoint of good pattern formation.
- the photopolymerization initiator in (C-1) means one that initiates polymerization by mainly generating radicals when irradiated with light in the ultraviolet to visible light range.
- Known photopolymerization initiators selected from acetophenone derivatives, benzophenone derivatives, benzoin ether derivatives, and xanthone derivatives are preferred from the viewpoint of the ability to use a general-purpose light source and rapid curing.
- photoinitiators examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexylphenylketone, isobutyl benzoin ether, benzoin methyl ether, thioxanthone, isopropylthioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1, and the like, but are not limited to these.
- the content of the photopolymerization initiator in (C-1) is not particularly limited, it is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (B). Within this range, it becomes easier to secure the interaction with the resin necessary for good pattern formation and the transmittance for obtaining appropriate sensitivity.
- the quinonediazide compound (C-2) includes a polyhydroxy compound in which a quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which a quinonediazide sulfonic acid is sulfonamide-bonded, and a polyhydroxypolyamino compound in which a quinonediazide sulfonic acid is ester-bonded. and/or known ones such as those with sulfonamide bonds. Although not all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may be substituted with quinonediazide, it is preferred that 40 mol % or more of all functional groups on average be substituted with quinonediazide. .
- the mole % of functional groups substituted with quinonediazide is referred to as the quinonediazide substitution rate.
- a quinone diazide compound By using such a quinone diazide compound, a positive photosensitive resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are general ultraviolet rays, can be produced. Obtainable.
- the polyhydroxy compound used here has two or more, preferably three or more phenolic hydroxyl groups in the molecule.
- Polyhydroxy compounds are, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ , BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML- PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML- HQ
- Polyamino compounds include, for example, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′- Examples include, but are not limited to, diaminodiphenyl sulfide and the like.
- polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.
- quinonediazide sulfonic acids include, but are not limited to, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,2-naphthoquinonediazide-5-sulfonic acid.
- a compound in which quinonediazide sulfonic acid is bound to a polyhydroxy compound is preferably used as the quinonediazide compound (C-2).
- a quinone diazide compound it is exposed to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of mercury lamps, which are general ultraviolet rays, and high sensitivity and higher resolution can be achieved.
- i-line wavelength 365 nm
- h-line wavelength 405 nm
- g-line wavelength 436 nm
- More preferred quinonediazide compounds (C-2) include compounds represented by formula (21) or formula (22).
- each Q independently represents a hydrogen atom, a group represented by structural formula (23), or a group represented by structural formula (24).
- each Q in formula (21) and formula (22) is independently represented by a hydrogen atom or a group represented by structural formula (21).
- the quinonediazide substitution rate is "(number of moles of quinonediazide sulfonic acid ester groups)/(number of moles of hydroxy groups before esterification of polyhydroxy compound) x 100" for polyhydroxy compounds, and "(quinonediazide sulfonic acid amide number of moles of groups)/(number of moles of amino groups before amidation of polyamino compound) x 100", in the case of polyhydroxypolyamino compounds ⁇ (number of moles of quinonediazide sulfonic acid ester groups) + (number of moles of quinonediazide sulfonic acid amide groups) ⁇ / ⁇ (number of moles of hydroxy groups before esterification of polyhydroxypolyamino compound)+(number of moles of amino groups of polyhydroxypolyamino compound before amidation) ⁇ 100".
- the quinonediazide substitution rate is obtained by multiplying the quinonediazide substitution rate of each quinonediazide compound by the ratio to all the quinonediazide compounds, as shown in the following formula, and totaling the values.
- the quinonediazide substitution rate of the quinonediazide compound in the photosensitive resin composition can be determined by removing the resin component of the photosensitive resin composition by a reprecipitation method or the like, separating the contained components by a column fractionation method or the like, and performing chemical analysis using NMR or IR. It can be obtained by identifying the structure.
- the method for producing the quinonediazide compound is not particularly limited, but a quinonediazide sulfonyl chloride (preferably quinonediazide sulfonyl chloride) is prepared by a conventional method in a solvent such as acetone, dioxane, tetrahydrofuran, or the like with sodium carbonate, sodium hydrogen carbonate, sodium hydroxide or water.
- a solvent such as acetone, dioxane, tetrahydrofuran, or the like with sodium carbonate, sodium hydrogen carbonate, sodium hydroxide or water.
- an inorganic base such as potassium oxide
- an organic base such as trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine, dicyclohexylamine
- the content of the quinonediazide compound (C-2) is not particularly limited. Part or more is more preferable. Moreover, 50 mass parts or less are preferable and 40 mass parts or less are more preferable. By setting the content of the quinonediazide compound within this range, photosensitivity can be obtained without impairing liquid repellency.
- the alkali-soluble resin (B) When used as a positive-type photosensitive resin composition containing the quinonediazide compound (C-2) as the photosensitive agent (C), the alkali-soluble resin (B) preferably contains a phenol resin and/or a polyhydroxystyrene resin. Also, two or more of these phenolic resins and/or polyhydroxystyrene resins may be used in combination.
- the quinonediazide compound (C-2) and the phenol resin and/or polyhydroxystyrene resin it is possible to reduce the amount of decrease in the thickness of the photosensitive resin dried product in the development step described later, so that polysiloxane (A) can be easily retained on the surface of the cured resin, and better liquid repellency can be obtained.
- Phenol resins include novolak phenol resins and resol phenol resins, and are obtained by polycondensing various phenol compounds alone or a mixture of a plurality of them using an aldehyde compound such as formalin by a known method.
- Phenolic compounds constituting novolac phenol resins and resole phenol resins include, for example, phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethyl phenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3- Dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-die
- Aldehyde compounds include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, and these can be used alone or in combination.
- polyhydroxystyrene resin it is also possible to use a vinylphenol homopolymer or a copolymer with styrene.
- Preferable weight average molecular weights of phenolic resins and polyhydroxystyrene resins are 2,000 to 20,000, preferably 3,000 to 10,000 in terms of polystyrene by GPC (gel permeation chromatography). Within this range, a high-concentration, low-viscosity resin composition can be obtained.
- the photosensitive resin composition is used as a positive-type photosensitive resin composition containing the quinonediazide compound (C-2) in the photosensitive agent (C), from the viewpoint of liquid repellency, 100 parts by mass of the alkali-soluble resin (B) , phenolic resin and/or polyhydroxystyrene resin in an amount of 20 parts by mass or more, more preferably 30 parts by mass or more. From the viewpoint of outgassing, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
- the photosensitive resin composition preferably contains an organic solvent (D).
- organic solvent (D) examples include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, alcohols, and other various known organic solvents.
- ethylene glycol monomethyl ether ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, ethers such as dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as " PGMEA”), 3-methoxybutyl acetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, dipropy
- the amount of the organic solvent (D) used is not particularly limited because it changes depending on the required thickness and the coating method to be adopted, but the solid content of the photosensitive resin composition (other components excluding the organic solvent (D) ) is preferably 100 to 2000 parts by mass, particularly preferably 150 to 900 parts by mass, based on 100 parts by mass.
- the photosensitive resin composition can further contain a thermal cross-linking agent.
- a thermal cross-linking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, and other known thermal cross-linking agents.
- the thermal cross-linking agent cross-links the alkali-soluble resin (B) or other components, and can enhance the durability of the cured resin.
- HMOM-TPPHBA HMOM-TPHAP
- NIKALAC registered trademark MX-290.
- NIKALAC MX-280 NIKALAC MX-270
- NIKALAC MX-279 NIKALAC MW-100LM
- NIKALAC MX-750LM all trade names, manufactured by Sanwa Chemical Co., Ltd.
- Examples of compounds having an epoxy group or an oxetanyl group include VG3101L (trade name, manufactured by Printec Co., Ltd.), "Tepic” (registered trademark) S, “Tepic” G, and “Tepic” P (trade names, Nissan Chemical Industries, Ltd.).
- the thermal cross-linking agent preferably has a phenolic hydroxyl group in one molecule and has a methylol group and/or an alkoxymethyl group at both ortho-positions of the phenolic hydroxyl group.
- the methylol group and/or the alkoxymethyl group are adjacent to the phenolic hydroxyl group, so that the durability of the cured resin can be further enhanced.
- alkoxymethyl groups include, but are not limited to, methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl groups.
- the content of the thermal cross-linking agent is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more with respect to 100 parts by mass of the total amount of the alkali-soluble resin (B). Moreover, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
- the content of the thermal cross-linking agent is 5 parts by mass or more, the heat resistance of the cured resin can be improved, and when the content is 50 parts by mass or less, the elongation of the cured resin can be prevented from decreasing.
- a method for manufacturing a photosensitive resin composition will be explained. For example, it can be obtained by dissolving the above polysiloxane (A) to photosensitizer (C) and other components in an organic solvent (D). Dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually 20°C to 80°C. In addition, the order of dissolving each component is not particularly limited, and for example, there is a method of dissolving compounds in order of low solubility.
- the obtained photosensitive resin composition is preferably filtered using a filtration filter to remove dust and particles.
- filter pore sizes include, but are not limited to, 1 ⁇ m, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, and 0.05 ⁇ m.
- Materials for the filtration filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and it is preferable to use polyethylene or nylon for filtration.
- a resin cured product is obtained by applying a photosensitive resin composition and drying it. Furthermore, by performing the following steps (1) to (4) in this order, it is possible to form a cured resin product in which at least a portion of the first electrode is open.
- a step of applying a photosensitive resin composition on a substrate having a first electrode to form a dried photosensitive resin product (2) A step of exposing the dried photosensitive resin product (3) Drying the exposed photosensitive resin Step of developing a product (4) Step of forming a cured resin product by heat-treating the developed photosensitive resin dried product
- a photosensitive resin composition is applied to a substrate having a first electrode, and a photosensitive Next, the process of forming a dry resin material will be described.
- Examples of methods for applying the photosensitive resin composition onto the substrate having the first electrode include spin coating, slit coating, dip coating, spray coating, and printing.
- the substrate to be coated with the photosensitive resin composition may be pretreated with the above-described adhesion improver.
- a solution obtained by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate is used.
- Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, vapor treatment, and the like.
- the coated photosensitive resin dried product is subjected to a reduced pressure drying treatment as necessary, and then using a hot plate, oven, infrared rays, etc., at a temperature in the range of 50 ° C. to 180 ° C. for 1 minute to several hours.
- a dried photosensitive resin product can be obtained by heat treatment.
- the dry photosensitive resin is irradiated with actinic rays through a photomask having a desired pattern.
- Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc.
- post-exposure baking may be performed. By performing post-exposure baking, effects such as an improvement in resolution after development and an increase in the allowable range of development conditions can be expected.
- the post-exposure bake temperature is preferably 50 to 180°C, more preferably 60 to 150°C.
- the post-exposure bake time is preferably 10 seconds to several hours. When the post-exposure baking time is within the above range, the reaction proceeds favorably, and the development time may be shortened. At this time, a grid-shaped cured product can be obtained by using a grid-shaped photomask.
- “half exposure” refers to a process in which a certain amount of undercoat of the dried photosensitive resin material is left in the exposed portion after completion of development. In other words, it refers to a process in which exposure is performed so that the lower layer of the dried photosensitive resin is not exposed.
- “Half-exposure” refers to a process in which a certain amount of undercoat of the dried photosensitive resin material is left in the exposed portion after completion of development. In other words, it refers to a process in which exposure is performed so that the lower layer of the dried photosensitive resin is not exposed.
- a portion of 10 can be formed by carrying out "half exposure” in which the lower layer of the dried photosensitive resin is exposed to a chemical dose that does not sensitize, followed by development and heat treatment.
- the thickness of the dried photosensitive resin that remains after completion of development can be adjusted.
- increasing the dose of chemical radiation reduces the thickness of the dried photosensitive resin material remaining after completion of development.
- increasing the dose of chemical radiation increases the thickness of the dried photosensitive resin material remaining after completion of development.
- Actinic radiation may be irradiated through a photomask having two or more areas with different transmittances to adjust the dose of actinic radiation.
- the surface of the cured product formed by half exposure has no liquid repellency and can have good ink applicability. That is, a cured product with a lyophobic surface and a cured product with a lyophilic surface can be formed by a single photolithography.
- the exposed dried photosensitive resin material is developed using a developer to remove areas other than the exposed areas.
- Developers include tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylamino Aqueous solutions of alkaline compounds such as ethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine are preferred.
- these alkaline aqueous solutions are added with a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination. good.
- a developing method methods such as spray, puddle, immersion, and ultrasonic waves are possible.
- alcohols such as ethanol and isopropyl alcohol
- esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.
- a cured product is obtained by a step of heat-treating the developed photosensitive resin dried product.
- the cured product of the photosensitive resin composition can be suitably used for partition walls of an organic EL display device.
- Heat treatment can remove residual solvents and components with low heat resistance, so that heat resistance and chemical resistance can be improved.
- a thermal cross-linking reaction can be advanced by heat treatment, and heat resistance and chemical resistance can be improved.
- a temperature is selected and the temperature is raised stepwise, or a certain temperature range is selected and the temperature is raised continuously for 5 minutes to 5 hours.
- One example is a method of heat-treating at 150° C. and 250° C. for 30 minutes each.
- a method of linearly raising the temperature from room temperature to 300° C. over 2 hours can be used.
- the heat treatment conditions in the present invention are preferably 180° C. or higher, more preferably 200° C. or higher, and even more preferably 230° C. or higher.
- the heat treatment conditions are preferably 400° C. or lower, more preferably 350° C. or lower, and even more preferably 300° C. or lower.
- a display device of the present invention includes the laminate of the present invention. Specific examples of display devices include LCDs and organic ELs.
- the cured resin material included in the laminate of the present invention has high liquid repellency on the surface of the cured material after UV ozone treatment, at least a part of the cured resin material on the first electrode is open. It can be suitably used for a display device in which a functional layer is formed by applying a functional ink inside by inkjet. For example, by forming an organic EL light-emitting layer containing at least one selected from organic EL light-emitting materials, hole injection materials, and hole transport materials, it can be used as an organic EL display device.
- the cured resin material included in the laminate of the present invention has F atoms inside the cured resin material, so that the water absorption of the cured resin material is reduced and the corrosion of the electrodes is suppressed, so that pixel shrinkage is small and durability is improved. It is possible to obtain a display device excellent in
- the cured resin material included in the laminate of the present invention has a small amount of outgassing at high temperatures, at least one selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material is used in the functional layer. It is preferably used for an organic EL display device including the above. An organic EL display device with small pixel shrinkage and excellent durability can be obtained.
- An organic EL display device has a drive circuit, a planarization layer, a first electrode, partition walls, an organic EL light emitting layer and a second electrode on a substrate.
- a substrate such as a glass or resin film is provided with TFTs and wirings located on the sides of the TFTs and connected to the TFTs, and unevenness is covered thereon.
- a planarization layer is thus provided, and a display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer.
- a first aspect of the manufacturing method of the display device of the present invention has steps (5) and (6) in this order.
- a step of forming a functional layer by applying a functional ink on the first electrode by inkjet (6) a step of forming a second electrode on the functional layer.
- a functional layer is formed by applying a functional ink onto the first electrode of the laminate of the present invention by inkjet.
- a composition containing at least one selected from the group consisting of an organic EL light-emitting material, a hole injection material, and a hole transport material is dropped into pixels as functional ink, and dried. It is possible to form an organic EL light-emitting layer. For drying, it is preferable to use a hot plate or an oven and heat at 150° C. to 250° C. for 0.5 to 120 minutes.
- a second electrode is formed on the functional layer. It is preferable that the second electrode is formed so as to entirely cover the partition wall and the functional layer. Examples of the method for forming the second electrode include a sputtering method and a vapor deposition method. In addition, it is preferable to form the second electrode with a uniform layer thickness without disconnection.
- a second aspect of the method for manufacturing a display device of the present invention includes step (7) and (8) in that order.
- step (7) In the laminate of the present invention, the step of forming a functional layer by applying a functional ink on the first electrode and the second step of the cured resin by inkjet to form a functional layer (8) on the functional layer forming a two-electrode formation;
- a functional layer is formed by applying a functional ink onto the first electrode of the laminate of the present invention and onto the second stage of the cured resin by inkjet.
- a composition containing at least one selected from the group consisting of an organic EL light-emitting material, a hole injection material, and a hole transport material is dropped into pixels as functional ink, and dried. It is possible to form an organic EL light-emitting layer. For drying, it is preferable to use a hot plate or an oven and heat at 150° C. to 250° C. for 0.5 to 120 minutes.
- a first electrode 8 patterned on a substrate and a cured resin material are laminated in this order, and a first step 9 defining an area where the cured resin material is to be inkjet-coated;
- a laminate having a second step 10 defining two or more pixel regions arranged in a region the first electrode 8 patterned on the substrate and the second step 10 of the cured resin are continuously formed. It can be suitably used for a method of manufacturing a display device in which the arranged functional layer 11 is formed by an inkjet coating method.
- a second electrode is formed on the functional layer. It is preferable that the second electrode is formed so as to entirely cover the partition wall and the functional layer. Examples of the method for forming the second electrode include a sputtering method and a vapor deposition method. In addition, it is preferable to form the second electrode with a uniform layer thickness without disconnection.
- Partition pattern 4 A partition pattern that exposes the first electrodes patterned on the substrate from the openings of the cured resin, the openings having a width of 70 ⁇ m and a length of 260 ⁇ m, and the openings formed by the cured resin.
- Partition pattern 5 A partition pattern that exposes the first electrode patterned on the substrate from the opening of the cured resin material, the opening having a width of 70 ⁇ m and a width of 70 ⁇ m.
- Partition pattern 12 having a length of 260 ⁇ m and having cured resins arranged at a pitch of 155 ⁇ m in the width direction and a pitch of 465 ⁇ m in the length direction.
- a second stage 10 of cured resin having a width a of 205 .mu.m and a first stage 9 of a cured resin having a width b of 85 .mu.m are formed so as to expose the first electrode 8 patterned on a substrate of 260 .mu.m.
- Arranged Partition Pattern First, the measurement method and the evaluation method will be described.
- the molecular weights of the alkali-soluble resins (b1) to (b3) synthesized in Synthesis Examples 4 to 6 were measured using the GPC apparatus described above and using N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a developing solvent. , the number average molecular weight (Mn) was calculated in terms of polystyrene.
- the measurement results of the PGMEA contact angle on the cured product were judged as follows, A being excellent, B being good, C being acceptable, and D being unsatisfactory.
- XPS X-ray photoelectron spectroscopy
- partition wall pattern 5 or the partition wall pattern 12 was formed using the cured product of the photosensitive resin composition was subjected to UV ozone resistance under the conditions of (3) UV ozone resistance evaluation described above. processed. Thereafter, in the case of partition pattern 5, an ink of a compound (HT-1) in which methyl benzoate was used as a solvent was used as a hole injection layer, and was surrounded by a cured resin using an inkjet device (Litlex 142 manufactured by ULVAC). After being dropped onto the first electrode 8 patterned on the substrate, it was baked at 200° C. to form a hole injection layer.
- HT-1 in which methyl benzoate was used as a solvent
- a compound (HT-2) with 4-methoxytoluene as a solvent is dropped onto the region surrounded by the cured resin using an inkjet device, and then baked at 190°C.
- a hole transport layer was formed.
- a mixture of the compound (GH-1) and the compound (GD-1) in which 4-methoxytoluene is used as a solvent is dropped onto the area surrounded by the cured resin using an inkjet device. It was baked at 130° C. to form a light-emitting layer.
- benzoin is applied as a hole injection layer on the first electrode 8 patterned on the substrate in the region sandwiched between the first stage of the cured resin and on the second stage 10 of the cured resin.
- An ink of compound (HT-1) using methyl acid as a solvent was continuously dropped using an inkjet device (Litlex 142 manufactured by ULVAC) and then baked at 200° C. to form a hole injection layer.
- a compound (HT-2) in which 4-methoxytoluene is used as a solvent is dropped onto the same area using an inkjet device, and then baked at 190° C. to form a hole-transporting layer. formed.
- a mixture of compound (GH-1) and compound (GD-1) with 4-methoxytoluene as a solvent was dropped onto the same region using an inkjet device, and then baked at 130°C. , to form a light-emitting layer.
- the compound (ET-1) and the compound (LiQ) as electron-transporting materials were successively laminated at a volume ratio of 1:1 by a vacuum vapor deposition method to form an organic EL layer 6 .
- Mg and Ag were vapor-deposited to a thickness of 10 nm at a volume ratio of 10:1 to form the second electrode 7 .
- a cap-shaped glass plate was adhered using an epoxy resin-based adhesive in a low-humidity nitrogen atmosphere for sealing, and a 5 mm square organic EL display device was fabricated on one substrate.
- the organic EL display device produced by the method described above was driven to emit light at 10 mA/cm 2 by direct current driving, and the initial light emitting area was observed. Furthermore, it was held at 80° C. for 500 hours, and was again caused to emit light by direct current driving at 10 mA/cm 2 , and it was confirmed whether there was any change in the light emitting area. , C was allowed and D was not allowed.
- composition analysis of cured resin A method for analyzing the components contained in the cured resin will be described, but any method that enables composition analysis may be used, and the method is not limited to the method described.
- ⁇ Preparation of cured resin for composition analysis> The photosensitive resin composition was applied onto an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Ltd.), and baked on a hot plate at 120° C. for 3 minutes. Then, using the above-described ACT-8 developing device, the film was developed using a 2.38% by mass TMAH aqueous solution, rinsed with distilled water, and dried by shaking off. Subsequently, the dried photosensitive resin after development was heated at 5° C. in a nitrogen atmosphere (oxygen concentration: 100 ppm or less) using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.).
- ACT-8 coating and developing apparatus
- the temperature was raised to 250°C at a rate of 1/min, and a heat curing step was performed in which heat treatment was performed at 250°C for 1 hour to prepare a resin cured product of the varnish.
- the thickness of the cured resin was about 2.0 ⁇ m.
- ⁇ Composition analysis by FT-IR> An infrared microscope Nicolet iN10 (manufactured by Thermo Fisher SCIENTIFIC) is used for the obtained resin cured product, and the detector uses MCT for the wave number range of 4000 to 650 cm ⁇ 1 , and the resolution is 8 cm ⁇ 1 , the IR spectrum was obtained by the single-reflection ATR method (Ge, 45°) in the measurement mode with 64 integration times.
- the injection port temperature was 300 ° C.
- the column flow rate was 1.5 mL / min
- the ionization method was EI (electron ionization)
- the mass range was m / z 10 to 800
- the scan speed was 0. Analysis was performed at 0.5 sec/scan.
- HMOM-TPHAP (compound represented by the following chemical formula, manufactured by Honshu Chemical Industry Co., Ltd.)
- VG3101L "Techmore” (registered trademark) VG3101L (compound represented by the following chemical formula, manufactured by Printec Co., Ltd.).
- Synthesis Example 1 Synthesis of polysiloxane (P-1) 39.80 g (0.17 mol) of TfTMS, 62.09 g (0.50 mol) of NapTMS, 13.12 g (0.10 mol) of TMSSucA, 15.66 g (0.23 mol) of MTMS, 131.05 g of MAK, and 14.56 g of IPA were charged, and stirred at 40°C while 27.90 g of water and 1.31 g of phosphoric acid (1.0 mass based on the charged monomers). %) mixed with phosphoric acid solution was added. After that, the flask was immersed in an oil bath at 70° C. and stirred for 60 minutes, and then the oil bath was heated to 130° C.
- Synthesis Example 2 Synthesis of acrylic liquid-repellent material (Ac-1) 100 g of cyclohexanone was added to a glass reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, and nitrogen gas was added. The temperature was raised to 110° C. under the atmosphere. Maintaining the temperature of cyclohexanone at 110° C., 44 g (0.65 mol) of N,N-dimethylacrylamide, 30 g (0.10 mol) of 2-(perfluorohexyl)ethyl methacrylate, 21 g (0.22 mol) of glycidyl methacrylate.
- Ac-1 acrylic liquid-repellent material
- Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was mixed with 100 mL of acetone, 17.4 g (0.3 mol) and cooled to -15°C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50°C.
- Synthesis Example 4 Synthesis of alkali-soluble resin (b1) Under a dry nitrogen stream, 88.8 g (0.20 mol) of 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride was dissolved in 500 g of NMP. . 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added to 100 g of NMP. and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours.
- Synthesis Example 5 Synthesis of alkali-soluble resin (b2) 62.0 g (0.20 mol) of 3,3′,4,4′-diphenylethertetracarboxylic dianhydride was dissolved in 500 g of NMP under a dry nitrogen stream. 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added to 100 g of NMP. and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours.
- Synthesis Example 7 Synthesis of quinonediazide compound (c2) Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g of 4-naphthoquinonediazide sulfonyl chloride. (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the inside of the reaction system did not reach 35° C. or higher. After dropping, the mixture was stirred at 30°C for 2 hours.
- TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
- the triethylamine salt was filtered and the filtrate drowned in water. After that, the deposited precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinonediazide compound (c2).
- the quinonediazide substitution rate of this naphthoquinonediazide compound was 83%.
- Synthesis Example 8 Synthesis of alkali-soluble resin (d1) Under dry nitrogen stream, 108.0 g (1.00 mol) of m-cresol, 75.5 g (0.93 mol of formaldehyde) of 37 wt% formaldehyde aqueous solution, oxalic acid dihydrate After charging 0.63 g (0.005 mol) of the compound and 264 g of methyl isobutyl ketone, the mixture was immersed in an oil bath, and a polycondensation reaction was carried out for 4 hours while refluxing the reaction solution.
- an alkali-soluble resin (d1) which is a novolac-type phenolic resin, was obtained.
- GPC gave a weight average molecular weight of 3,500.
- FIG. 1 shows a schematic diagram of the laminate used for evaluation.
- An ITO transparent conductive film of 10 nm was formed on the non-alkali glass plate 1 over the entire surface of the non-alkali glass plate by sputtering, and etched as the first electrode 8 patterned on the substrate. At the same time, an auxiliary electrode 3 was also formed to lead out the second electrode.
- the resulting substrate was ultrasonically cleaned with "Semico Clean” (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, then washed with ultrapure water and dried to obtain an intermediate for evaluation.
- each component was mixed at the compounding ratio shown in Table 1, and thoroughly stirred at room temperature to dissolve. After that, the resulting solution was filtered through a filter with a pore size of 0.45 ⁇ m to obtain photosensitive resin compositions W1 to W12.
- the obtained photosensitive resin compositions W1 to W12 are applied to the evaluation intermediate by a spin coating method, and prebaked on a hot plate at 120 ° C. for 2 minutes to form a photosensitive resin having a thickness of about 2 ⁇ m.
- After forming the dried product it was irradiated with ultraviolet rays of 120 mJ/cm 2 (converted to h-rays) at all wavelengths of a mercury lamp through a photomask having a predetermined pattern, and then treated with a 2.38% by mass TMAH aqueous solution for 60 seconds. After development and rinsing with water, two sheets each of which formed an uncured material of the partition pattern 4 and an uncured material of the partition pattern 5 were produced.
- Example 7 Laminate A having partition wall pattern 4 described in Example 1 was prepared using photosensitive resin composition W3, and (4-3) the cured resin surface and the interior were evaluated by XPS comparison.
- a resin cured product of the photosensitive resin composition W3 is referred to as a resin cured product W3.
- FIG. 6 shows the C1s spectrum 22 of the surface of the cured resin W3 and the C1s spectrum 23 of the inside of the cured resin W3.
- the peak height of the peak derived from CF 2 group having a peak top within the binding energy range of 290 to 292 eV was higher in the C1s spectrum 22 of the resin cured product W3 surface.
- the C1s spectrum 23 inside the resin cured product W3 had a higher peak height of the peak derived from the CF 3 group having a peak top within the range of 292 to 294 eV in binding energy.
- the resin cured product W3 had high liquid repellency after the UV ozone treatment, resulting in high durability when used in a display device.
- Comparative example 5 Using the photosensitive resin composition W10, a substrate on which the partition wall pattern 4 was formed as described in Example 1 was prepared, and (4-3) the cured resin surface and the inside were evaluated by XPS comparison.
- a cured resin product of the photosensitive resin composition W10 is referred to as a cured resin product W10.
- FIG. 7 shows the C1s spectrum 24 of the surface of the cured resin W10 and the C1s spectrum 25 of the inside of the cured resin W10.
- a comparison of the C1s spectrum 24 of the surface of the cured resin W10 and the C1s spectrum 25 of the cured resin W10 internal revealed that the height of the peak derived from the CF2 group and the peak derived from the CF3 group were the same.
- the resin cured product W10 was poorly evaluated for liquid repellency.
- Example 8 Comparative Examples 6 and 7 IR spectra of cured resins formed from photosensitive resin compositions W3 (Example 8), W7 (Comparative Example 6) and W8 (Comparative Example 7) by the method described in ⁇ Composition analysis by FT-IR>. It was measured.
- the IR spectra of the cured resins of the photosensitive resin compositions W3 and W7 gave peaks at 1775 to 1780 cm ⁇ 1 and 1720 to 1725 cm ⁇ 1 derived from the carbonyl group stretching vibration in the imide ring structure.
- the IR spectrum of the resin cured product of the photosensitive resin composition W8 did not show any spectrum that would indicate the existence of the imide ring structure.
- the thermal decomposition products of the resin cured products of the photosensitive resin compositions W3, W7 and W8 were analyzed by the method described in ⁇ Composition Analysis by Thermal Decomposition GC/MS>. As a result of the analysis, a peak (840 to 850 seconds) attributed to the imide ring structure was obtained from the cured resins of the photosensitive resin compositions W3 and W7. On the other hand, no peak attributed to the imide ring structure was observed from the cured product of the photosensitive resin composition W8.
- the evaluation result of (5) durability of the photosensitive resin composition W3 used in Example 8 was that of Example 3, and there was no change in the light emitting area, and the judgment was A.
- the evaluation result of (5) durability of the photosensitive resin composition W7 used in Comparative Example 6 was Comparative Example 1, and the light emitting area was reduced to 83%, so the judgment was C.
- the presence of an imide ring structure could be confirmed from the resin cured product of the photosensitive resin composition W7, the XPS analysis of the (4-2) resin cured product of Comparative Example 1 showed that the fluorine atom was 0 atom%. Presumed to have shrunk.
- Examples 9 and 10 The thermal decomposition products of the cured resin compositions W3 (Example 9) and W6 (Example 10) were analyzed by the method described in ⁇ Composition Analysis by Thermal Decomposition GC/MS>. As a result of the analysis, a peak attributed to indene (450 to 455 seconds) was obtained from the cured resin of the photosensitive resin composition W3. On the other hand, no peak attributed to indene was observed from the resin cured product of the photosensitive resin composition W6.
- the photosensitive resin compositions W3 and W6 were applied onto the substrate by spin coating, and prebaked on a hot plate at 120° C. for 2 minutes to form a dried photosensitive resin having a thickness of about 2 ⁇ m.
- "half-exposure" was performed by irradiating ultraviolet rays of all wavelengths of a mercury lamp so that half the area of the dried photosensitive resin material had a thickness of 0.5 ⁇ m after development. The remaining half of the area was left unexposed to prevent the thickness from being reduced during the development process with the W3 photosensitive resin dried material having positive photosensitive characteristics.
- W6 which has a negative type photosensitive characteristic
- W6 was irradiated with ultraviolet rays at an exposure amount of 120 mJ/cm 2 (converted to h-line) so as not to reduce the thickness during the development process.
- the film was developed with a 2.38% by mass TMAH aqueous solution for 60 seconds, and then rinsed with water to prepare an intermediate with a dried photosensitive resin.
- TMAH 2.38% by mass TMAH aqueous solution for 60 seconds
- the obtained intermediate with the dried photosensitive resin is heated in a nitrogen atmosphere for 1 hour to cure the resin.
- a laminate B with objects was created.
- the contact angle with PGMEA measured on the surface of the cured resin of the photosensitive resin composition W3 was 46° in the unexposed area and 5° or less in the half-exposed area. Thus, it was confirmed that the surface of the cured resin obtained by half-exposure of the photosensitive resin composition containing the compound having indene exhibited lyophilicity. That is, a cured resin product with a liquid-repellent surface and a cured resin product with a lyophilic surface can be formed by a single photolithography.
- the contact angle with PGMEA measured on the surface of the cured resin of the photosensitive resin composition W6 was 46° in the exposed area and 40° in the half-exposed area, and liquid repellency was confirmed in both areas. .
- FIG. 1 shows a schematic diagram of the laminate used for evaluation.
- An ITO transparent conductive film of 10 nm was formed on the non-alkali glass plate 1 over the entire surface of the non-alkali glass plate by sputtering, and etched as the first electrode 8 patterned on the substrate. At the same time, an auxiliary electrode 3 was also formed to lead out the second electrode.
- the resulting substrate was ultrasonically cleaned with "Semico Clean” (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, then washed with ultrapure water and dried to obtain an intermediate for evaluation.
- the obtained photosensitive resin composition W3 is applied by a spin coating method, and prebaked on a hot plate at 120 ° C. for 2 minutes to obtain a photosensitive resin dried product having a thickness of about 2 ⁇ m. formed.
- a photosensitive resin dried product having a thickness of about 2 ⁇ m. formed.
- 2 The film was developed with a 38% by mass TMAH aqueous solution for 60 seconds and rinsed with water to form an uncured product of the partition pattern 12 .
- the substrate on which the partition pattern 12 is formed is cured by heating at 250° C. for 1 hour in a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) to form the partition pattern 12 .
- Got body A The formed partition pattern 12 had a first step thickness of 1.8 ⁇ m and a second step thickness of 0.5 ⁇ m.
- the surface of the cured resin W3 (second stage) formed by half-exposure is lyophilic, and in the evaluation of (5) durability, as shown in FIG. And, the functional ink 11 could be continuously dropped on the second stage 10 of the cured resin without white spots.
- Example 12 Evaluation was performed in the same manner as in Example 11, except that the photosensitive resin composition was changed to W5.
- the photosensitive resin composition was changed to W5.
- Table 3 shows the element concentrations (atom %) of F atoms and Si atoms.
- FIG. 9 shows the C1s spectrum 27 of the surface of the cured resin W5 (second stage) formed by half exposure. Table 3 shows the evaluation results of (5) durability.
- the result of XPS analysis of the surface of the cured resin material W5 (second stage) formed by half exposure satisfied the characteristic (v).
- the surface of the cured resin W5 (second stage) formed by half-exposure is lyophilic, and in the evaluation of (5) durability, as shown in FIG. And, the functional ink 11 could be continuously dropped on the second stage 10 of the cured resin without white spots.
- Example 13 Evaluation was performed in the same manner as in Example 11, except that the method for forming the partition pattern 12 was changed as follows.
- the photosensitive resin composition W10 was applied onto the evaluation intermediate by spin coating, and prebaked on a hot plate at 120° C. for 2 minutes to form a dried photosensitive resin having a thickness of about 0.6 ⁇ m.
- the film was developed with a 2.38% by mass TMAH aqueous solution for 50 seconds, followed by water.
- the photosensitive resin composition W3 was applied by a spin coating method and prebaked on a hot plate at 120° C. for 2 minutes to form a dried photosensitive resin having a thickness of about 2.0 ⁇ m.
- the film was developed with a 2.38% by mass TMAH aqueous solution for 60 seconds, followed by water. rinsed with Next, using a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) at 250° C., heating is performed for 1 hour in a nitrogen atmosphere to cure the first electrode and the second cured resin material as shown in FIG. A first step 9 of a cured resin material was formed on the step 10, and two laminates A were formed in which the partition pattern 12 was formed.
- the formed partition pattern 12 had a first step thickness of 1.8 ⁇ m and a second step thickness of 0.5 ⁇ m.
- the XPS analysis result of the surface of the cured resin W10 (second stage) was a result that satisfied the characteristic (v).
- the surface of the cured resin W10 (second stage) is lyophilic, and in the evaluation of (5) durability, as shown in FIG. It was possible to drop the functional ink 11 continuously onto the second stage 9 without white voids.
- Example 14 Evaluation was performed in the same manner as in Example 13, except that the photosensitive resin composition was changed to the type shown in Table 3.
- Table 3 shows the element concentrations (atom %) of F atoms and Si atoms obtained by XPS analysis of the (4-1) surface of the cured resin in the first and second stages.
- FIG. 11 shows the C1s spectrum 29 of the surface of the cured resin W10, which is the second stage.
- Table 3 shows the evaluation results of (5) durability.
- the XPS analysis result of the surface of the cured resin W10 (second stage) was a result satisfying the characteristic (v).
- the surface of the cured resin W10 (second stage) is lyophilic, and in the evaluation of (5) durability, as shown in FIG. It was possible to drop the functional ink 11 continuously onto the second stage 9 without white voids.
- Example 14 showed a reduction in the light emitting area in the durability evaluation of the display device.
- the photosensitive resin composition W8 used in the first step the analysis of the inside of the cured resin by XPS in Comparative Example 2 revealed that the concentration of F atoms was 0 atom %, so it is presumed that the emission area was reduced.
- Example 16 Evaluation was performed in the same manner as in Example 11, except that the photosensitive resin composition was changed to W11.
- the photosensitive resin composition was changed to W11.
- Table 3 shows the element concentrations (atom %) of F atoms and Si atoms.
- FIG. 12 shows the C1s spectrum 31 of the surface of the cured resin W5 (second stage) formed by half exposure. Table 3 shows the evaluation results of (5) durability.
- the surface of the cured resin W11 (second stage) formed by half exposure is lyophilic, and (5) in durability evaluation, as shown in FIG. And, the functional ink 11 could be continuously dropped on the second stage 10 of the cured resin without white spots.
- Example 17 Evaluation was performed in the same manner as in Example 13, except that the photosensitive resin composition was changed to the type shown in Table 3.
- Table 3 shows the element concentrations (atom %) of F atoms and Si atoms obtained by XPS analysis of the (4-1) surface of the cured resin in the first and second stages.
- FIG. 13 shows the C1s spectrum 32 of the surface of the cured resin W10, which is the second stage.
- Table 3 shows the evaluation results of (5) durability.
- the XPS analysis result of the surface of the cured resin W10 (second stage) was a result satisfying the characteristic (v).
- the surface of the cured resin W10 (second stage) is lyophilic, and in the evaluation of (5) durability, as shown in FIG. It was possible to drop the functional ink 11 continuously onto the second stage 9 without white voids.
- Example 17 showed a reduction in the light emitting area in the durability evaluation of the display device.
- the photosensitive resin composition W12 used in the first step the analysis of the inside of the cured resin by XPS in Comparative Example 8 revealed that the concentration of F atoms was 0 atom %, so it is presumed that the emission area was reduced.
- Non-alkali glass substrate 3 Auxiliary electrode 4 Partition pattern 5 Partition pattern 6 Organic EL layer 7
- Second electrode 8 First electrode 9 patterned on substrate First step 10 of cured resin Second step 11 of cured resin Functional layer 12 Partition wall pattern 13
- Substrate 14 Flattening layer 16
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Abstract
Description
基板、該基板上にパターンニングされた第1電極、樹脂硬化物の順に積層され、前記第1電極上にある前記樹脂硬化物の少なくとも一部が開口している積層体であって、
X線光電子分光法(XPS)による前記樹脂硬化物の分析が特性(i)および特性(ii)を満たす積層体。
(i)前記第1電極と前記樹脂硬化物が接する界面と反対側の表面の少なくとも一部から測定される前記樹脂硬化物のF原子の濃度が8.1atom%以上30.0atom%以下、及び、Si原子の濃度が1.0atom%以上6.0atom%以下である
(ii)前記第1電極と前記樹脂硬化物が接する界面に対して垂直、且つ前記基板から前記樹脂硬化物の方向であり、前記第1電極と前記樹脂硬化物が接する界面を起点に100~200nmの範囲のいずれかで測定される前記樹脂硬化物のF原子の濃度が0.1atom%以上8.0atom%以下である
<積層体>
本発明の積層体は、基板、該基板上にパターンニングされた第1電極、樹脂硬化物の順に積層され、前記第1電極上にある前記樹脂硬化物の少なくとも一部が開口している積層体であって、
X線光電子分光法(XPS)による前記樹脂硬化物の分析が特性(i)および特性(ii)を満たす積層体である。
(i)前記第1電極と前記樹脂硬化物が接する界面と反対側の表面の少なくとも一部から測定される前記樹脂硬化物のF原子の濃度が8.1atom%以上30.0atom%以下、及び、Si原子の濃度が1.0atom%以上6.0atom%以下である。
(ii)前記第1電極と前記樹脂硬化物が接する界面に対して垂直、且つ前記基板から前記樹脂硬化物の方向であり、前記第1電極と前記樹脂硬化物が接する界面を起点に100~200nmの範囲のいずれかで測定される前記樹脂硬化物のF原子の濃度が0.1atom%以上8.0atom%以下である。
前記樹脂硬化物の、前記第1電極と前記樹脂硬化物が接する界面と反対側の表面の少なくとも一部から測定される前記樹脂硬化物のC1sスペクトル[A]と、
前記第1電極と樹脂硬化物が接する界面に対して垂直、且つ前記基板から樹脂硬化物の方向であり、第1電極と樹脂硬化物が接する界面を起点に100~200nmの範囲のいずれかで測定される前記樹脂硬化物のC1sスペクトル[B]が、
特性(iii)および特性(iv)を満たすことが好ましい。
(iii)C1sスペクトル[B]における結合エネルギー290~292eVの範囲内にピークトップがあるCF2基由来のピークのピーク高さより、C1sスペクトル[A]における同ピーク高さの方が高い。
(iv)C1sスペクトル[A]における結合エネルギー292~294eVの範囲内にピークトップがあるCF3基由来のピークのピーク高さより、C1sスペクトル[B]における同ピーク高さの方が高い。
(v)前記樹脂硬化物の、前記第1電極と樹脂硬化物が接する界面と反対側の表面の少なくとも一部から測定されるF原子の濃度が0.1atom%以上20.0atom%以下、及び、Si原子の濃度が0.1atom%以上0.9atom%以下であり、且つ、C1sスペクトルにおける結合エネルギー290~295eVの範囲に測定される最大ピーク高さを持つピークが、292~294eVの範囲内にピークトップがあるCF3基由来のピークである。
(I)式(3)で示される繰り返し単位構造および/または式(4)で示される繰り返し単位構造
(II)式(5)で示される繰り返し単位構造および/または式(6)で示される繰り返し単位構造
Σ((あるキノンジアジド化合物のキノンジアジド置換率)×(全キノンジアジド化合物に対するあるキノンジアジド化合物の割合))
また、感光性樹脂組成物中のキノンジアジド化合物のキノンジアジド置換率は、感光性樹脂組成物の樹脂成分を再沈殿法などで除去後、カラム分取法などで含有成分を分離し、NMRやIRで化学構造を同定することにより求めることができる。
(1)第1電極を有する基板上に感光性樹脂組成物を塗布し感光性樹脂乾燥物を形成する工程
(2)前記感光性樹脂乾燥物を露光する工程
(3)露光した感光性樹脂乾燥物を現像する工程
(4)現像した感光性樹脂乾燥物を加熱処理することで樹脂硬化物を形成する工程
まず、(1)第1電極を有する基板に感光性樹脂組成物を塗布し、感光性樹脂乾燥物を形成する工程を説明する。
<表示装置>
本発明の表示装置は、本発明の積層体を具備する。表示装置の具体例としては、LCD、有機EL、などが挙げられる。
本発明の表示装置の製造方法の第一の態様は、工程(5)および(6)をこの順に有する。
(5)本発明の積層体において、前記第1電極上に機能性インクをインクジェットで塗布して機能層を形成する工程
(6)該機能層上に第2電極を形成する工程。
(7)本発明の積層体において、前記第1電極上および前記樹脂硬化物の第2段上に機能性インクをインクジェットで塗布して機能層を形成する工程
(8)該機能層上に第2電極形成を形成する工程。
隔壁パターン4:樹脂硬化物の開口部から基板上にパターンニングされた第1電極を露出せしめる隔壁パターンであって、開口部の大きさが幅70μmおよび長さ260μmであり、開口部が樹脂硬化物の中央に一カ所配置された隔壁パターン
隔壁パターン5:樹脂硬化物の開口部から基板上にパターンニングされた第1電極を露出せしめる隔壁パターンであって、開口部の大きさが幅70μmおよび長さ260μmであり、幅方向にピッチ155μmおよび長さ方向にピッチ465μmで樹脂硬化物が配置された隔壁パターン
隔壁パターン12:図2または図3に記載の隔壁パターンであり、幅70μmおよび長さ260μmの基板上にパターンニングされた第1電極8を露出せしめるように、幅aが205μmである樹脂硬化物の第2段10と、幅bが85μmである樹脂硬化物の第1段9を配置した隔壁パターン
まず、測定方法および評価方法について説明する。
合成例1で合成したポリシロキサン(P-1)、合成例2で合成したアクリル系撥液材(Ac-1)、合成例8で合成したアルカリ可溶性樹脂(d1)、及び合成例9で合成したアルカリ可溶性樹脂(Ac-2)の分子量は、GPC(ゲルパーミエーションクロマトグラフィー)装置(Waters2690-996;日本ウォーターズ(株)製)を用い、展開溶媒をテトラヒドロフランとして測定し、ポリスチレン換算で重量平均分子量(Mw)を算出した。
接触角の測定には、後述の方法で図1における隔壁パターン4を有する積層体を形成し、隔壁パターン4の樹脂硬化物上に、3μLのPGMEAを滴下し接触角を測定した。測定には、接触角測定装置(DMs-401;協和界面科学(株)製)を用いて、JIS-R3257:1999に準拠し、23℃で静滴法にて測定した。
A:接触角が45°以上
B:接触角が35°以上45°未満
C:接触角が25°以上35°未満
D:接触角が25°未満。
前述の(2)撥液性の評価を行った積層体に下記条件でUVオゾン処理を行った。その後、隔壁パターン4の樹脂硬化物上に、3μLのPGMEAを滴下し接触角を測定した。測定には、接触角測定装置(DMs-401;協和界面科学(株)製)を用いて、JIS-R3257に準拠し、23℃で静滴法にて測定した。
装置:PL16 (SEN LIGHTS Corp.製)
照度:15mW/cm2
照射距離:75mm
照射時間:120sec
(4)X線光電子分光法(XPS)による樹脂硬化物の分析
X線光電子分光法(XPS)による樹脂硬化物の分析方法を示す。
後述の方法で図1における隔壁パターン4を形成した積層体を作成し、隔壁パターン4における樹脂硬化物の開口部の端から100μmの範囲のいずれかの箇所でXPS分析を行った。
(4-1)樹脂硬化物表面のXPS分析 特性(i)、特性(v)の測定方法
図1における隔壁パターン4または隔壁パターン12の樹脂硬化物の表面から、下記に記載の測定条件でX線光電子分光法(XPS)による分析を行った。測定条件、データ処理条件を下記に記載する。
装置 Quantera SXM (PHI 社製)
励起X線 monochromatic Al K 1,2 線(1486.6 eV)
X線径 200μm
光電子検出角度 45°(試料表面に対する検出器の傾き)
・データ処理条件
スムージング 9-point smoothing
横軸補正 C1s メインピーク(CHx, C-C,C=C)を284.6 eVとした。
図1における隔壁パターン4の樹脂硬化物に対して、パターンニングされた第1電極8と隔壁パターン4の樹脂硬化物が接する界面に対して垂直、且つ無アルカリガラス基板1から隔壁パターン4の方向であり、パターンニングされた第1電極8と隔壁パターン4の樹脂硬化物が接する界面を起点に100~200nmの範囲のいずれかが暴露されるようにArガスクラスターイオン(Ar-GCIB)を行った。その後、Ar-GCIBを行った箇所でX線光電子分光法(XPS)の分析を行った。測定条件、データ処理を下記に記載する。
装置 K-Alpha(Thermo Fisher Scientific社製)
励起X線 monochromatic Al K 1,2 線(1486.6 eV)
X線径 400 μm
光電子脱出角度 90°(試料表面に対する検出器の傾き)
イオンエッチング条件 Arガスクラスターイオン(Ar-GCIB)
エッチングレート 3.5nm/min
・データ処理
スムージング 11-point smoothing
横軸補正 C1sメインピーク(CHx, C-C)を284.6 eVとした。
図1における隔壁パターン4の樹脂硬化物の表面から、下記に記載の測定条件でX線光電子分光法(XPS)による分析を行った。続いて、隔壁パターン4の樹脂硬化物に対して、パターンニングされた第1電極8と隔壁パターン4の樹脂硬化物が接する界面に対して垂直、且つ無アルカリガラス基板1から隔壁パターン4の方向であり、パターンニングされた第1電極8と隔壁パターン4の樹脂硬化物が接する界面を起点に100~200nmの範囲のいずれかが暴露されるようにArガスクラスターイオン(Ar-GCIB)を行った。その後、Ar-GCIBを行った箇所でX線光電子分光法(XPS)の分析を行った。測定条件、データ処理を下記に記載する。
装置 K-Alpha(Thermo Fisher Scientific社製)
励起X線 monochromatic Al K 1,2 線(1486.6 eV)
X線径 400 μm
光電子脱出角度 90°(試料表面に対する検出器の傾き)
イオンエッチング条件 Arガスクラスターイオン(Ar-GCIB)
エッチングレート 3.5nm/min
・データ処理
スムージング 11-point smoothing
横軸補正 C1sメインピーク(CHx, C-C)を284.6 eVとした。
(5)耐久性の評価
感光性樹脂組成物の硬化物を用いて隔壁パターン5または隔壁パターン12を形成した図1の積層体に、前述の(3)UVオゾン耐性の評価の条件でUVオゾン処理を行った。その後、隔壁パターン5の場合、正孔注入層として、安息香酸メチルを溶媒とした化合物(HT-1)のインキを、インクジェット装置(ULVAC社製Litlex142)を用いて、樹脂硬化物に囲まれた基板上にパターンニングされた第1電極8上に滴下したのち、200℃で焼成し、正孔注入層を形成した。次に、正孔輸送層として、4-メトキシトルエンを溶媒とした化合物(HT-2)を、インクジェット装置を用いて、樹脂硬化物に囲まれた領域に滴下したのち、190℃で焼成し、正孔輸送層を形成した。さらに、発光層として、4-メトキシトルエンを溶媒とした化合物(GH-1)と化合物(GD-1)の混合物を、インクジェット装置を用いて、樹脂硬化物に囲まれた領域に滴下したのち、130℃で焼成し、発光層を形成した。隔壁パターン12の場合、樹脂硬化物の第1段で挟まれた領域にある基板上にパターンニングされた第1電極8上および樹脂硬化物の第2段10上に正孔注入層として、安息香酸メチルを溶媒とした化合物(HT-1)のインキを、インクジェット装置(ULVAC社製Litlex142)を用いて、連続して滴下したのち、200℃で焼成し、正孔注入層を形成した。次に、正孔輸送層として、4-メトキシトルエンを溶媒とした化合物(HT-2)を、インクジェット装置を用いて、同様の領域に滴下したのち、190℃で焼成し、正孔輸送層を形成した。さらに、発光層として、4-メトキシトルエンを溶媒とした化合物(GH-1)と化合物(GD-1)の混合物を、インクジェット装置を用いて、同様の領域に滴下したのち、130℃で焼成し、発光層を形成した。
A:発光面積に変化無し
B:発光面積が90%~99%に変化
C:発光面積が80%~89%に変化
D:発光面積が79%以下に変化
(6)樹脂硬化物の組成分析
樹脂硬化物中に含まれる成分の分析方法を示すが、組成分析が可能な手法であれば良く、記載の手法に限定されるものではない。
感光性樹脂組成物を塗布現像装置ACT-8(東京エレクトロン(株)製)を用いて、8インチシリコンウェハ上にスピンコート法で塗布し、120℃で3分間ホットプレートにてベークをした。その後、前記ACT-8の現像装置を用いて、2.38質量%TMAH水溶液を用いて現像し、蒸留水でリンス後、振り切り乾燥した。続いて、現像後の感光性樹脂乾燥物を、高温イナートガスオーブン(INH-9CD-S;光洋サーモシステム(株)製)を用いて、窒素雰囲気下(酸素濃度:100ppm以下)にて、5℃/分で250℃まで昇温し、250℃で1時間加熱処理する熱硬化工程を行い、ワニスの樹脂硬化物を作製した。その樹脂硬化物の厚さは約2.0μmであった。
<FT-IRによる組成分析>
得られた樹脂硬化物に対して、赤外顕微鏡Nicolet iN10(Thermo Fisher SCIENTIFIC製)を使用して、波数4000~650cm-1の範囲に対して、検出器はMCTを使用し、分解能は8cm-1とし、積算回数64回にて、測定モードは1回反射ATR法(Ge、45°)によりIRスペクトルを得た。
得られた樹脂硬化物に対して、マルチショット・パイロライザー PY-3030D(フロンティアラボ製)を使用して、加熱温度600℃の条件で、熱分解を行い、ガスクロマトグラフ質量分析計JMS-Q1050GC(日本電子製)を使用して、GCカラムはステンレスキャピラリーカラム(0.25mm内径×30m、固定相;5%フェニルポリジメチルシロキサン)を用い、GC温度は40℃(3分保持)から20℃/分の速度で320℃まで昇温し、注入口温度は300℃、カラム流量は1.5mL/分、イオン化法はEI(電子イオン化)法、質量数範囲はm/z10~800とし、スキャン速度0.5sec/scanとして分析を行った。
MTMS:メチルトリメトキシシラン
NapTMS:1-ナフチルトリメトキシシラン
TMSSucA:3-トリメトキシシリルプロピルコハク酸無水物
TfTMS:トリデカフルオロオクチルトリメトキシシラン
<架橋剤>
HMOM-TPHAP:(下記化学式に示す化合物、本州化学工業(株)製)
PGMEA:プロピレングリコールモノメチルエーテルアセテート
PGME:プロピレングリコールモノメチルエーテル
MAK:2-ヘプタノン
IPA:イソプロピルアルコール
実施例および比較例で用いた化合物について以下に示す。
500mLの三口フラスコにTfTMSを39.80g(0.17mol)、NapTMSを62.09g(0.50mol)、TMSSucAを13.12g(0.10mol)、MTMSを15.66g(0.23mol)、MAKを131.05g、IPAを14.56g仕込み、40℃で攪拌しながら水27.90g、リン酸1.31g(仕込みモノマーに対して1.0質量%)を混和したリン酸溶液を添加した。その後、フラスコを70℃のオイルバスに浸けて60分間攪拌した後、オイルバスを15分間かけて130℃まで昇温した。昇温開始10分後に溶液の内温が100℃に到達し、そこから1時間加熱攪拌し(内温は100~125℃)、ポリシロキサン(P-1)を得た。なお、昇温および加熱攪拌中、窒素を0.07l(リットル)/分で流した。GPCを用いて重量平均分子量を求めた結果、重量平均分子量3000であった。
撹拌装置、還流冷却管、滴下ロート、温度計および窒素ガス吹き込み口を備えたガラス製の反応容器に、シクロヘキサノンを100g加えて、窒素ガス雰囲気下で110℃に昇温した。シクロヘキサノンの温度を110℃に維持し、N,N-ジメチルアクリルアミド44g(0.65モル)、2-(パーフルオロヘキシル)エチルメタクリレート30g(0.10モル)、グリシジルメタクリレート21g(0.22モル)、3-フェノキシベンジルアクリレート5g(0.03モル)からなるモノマー混合溶液を滴下ロートにより2時間で等速滴下して、各モノマー溶液を調製した。滴下終了後、モノマー溶液を、115℃まで昇温させ、2時間反応させてアクリル系撥液材(Ac-1)を得た。GPCを用いて重量平均分子量を求めた結果、重量平均分子量5500であった。
2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン18.3g(0.05モル)をアセトン100mL、プロピレンオキシド17.4g(0.3モル)に溶解させ、-15℃に冷却した。ここに3-ニトロベンゾイルクロリド20.4g(0.11モル)をアセトン100mLに溶解させた溶液を滴下した。滴下終了後、-15℃で4時間反応させ、その後室温に戻した。析出した白色固体をろ別し、50℃で真空乾燥した。
乾燥窒素気流下、2,2-(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン二無水物88.8g(0.20モル)をNMP500gに溶解させた。ここに合成例3で得られたヒドロキシル基含有ジアミン化合物96.7g(0.16モル)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン1.24g(0.005モル)をNMP100gとともに加えて、20℃で1時間反応させ、次いで50℃で2時間反応させた。次に末端封止剤として3-アミノフェノール8.7g(0.08モル)をNMP50gとともに加え、50℃で2時間反応させた。その後、N,N-ジメチルホルムアミドジメチルアセタール47.7g(0.40モル)をNMP100gで希釈した溶液を投入した。投入後、50℃で3時間撹拌した。撹拌終了後、溶液を室温まで冷却した後、溶液を水5Lに投入して白色沈殿を得た。この沈殿を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、目的のポリイミド前駆体であるアルカリ可溶性樹脂(b1)を得た。アルカリ可溶性樹脂(b1)の数平均分子量は12000であった。
乾燥窒素気流下、3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物62.0g(0.20モル)をNMP500gに溶解させた。ここに合成例3で得られたヒドロキシル基含有ジアミン化合物96.7g(0.16モル)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン1.24g(0.005モル)をNMP100gとともに加えて、20℃で1時間反応させ、次いで50℃で2時間反応させた。次に末端封止剤として3-アミノフェノール8.7g(0.08モル)をNMP50gとともに加え、50℃で2時間反応させた。その後、N,N-ジメチルホルムアミドジメチルアセタール47.7g(0.40モル)をNMP100gで希釈した溶液を投入した。投入後、50℃で3時間撹拌した。撹拌終了後、溶液を室温まで冷却した後、溶液を水5Lに投入して白色沈殿を得た。この沈殿を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、目的のポリイミド前駆体であるアルカリ可溶性樹脂(b2)を得た。アルカリ可溶性樹脂(b2)の数平均分子量は11000であった。
乾燥窒素気流下、3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物62.0g(0.20モル)をNMP500gに溶解させた。ここにビス(3-アミノ-4-ヒドロキシフェニル)スルホン44.85g(0.16モル)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン1.24g(0.005モル)をNMP100gとともに加えて、20℃で1時間反応させ、次いで50℃で2時間反応させた。次に末端封止剤として3-アミノフェノール8.7g(0.08モル)をNMP50gとともに加え、50℃で2時間反応させた。その後、N,N-ジメチルホルムアミドジメチルアセタール47.7g(0.40モル)をNMP100gで希釈した溶液を投入した。投入後、50℃で3時間撹拌した。撹拌終了後、溶液を室温まで冷却した後、溶液を水5Lに投入して白色沈殿を得た。この沈殿を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、目的のポリイミド前駆体であるアルカリ可溶性樹脂(b3)を得た。アルカリ可溶性樹脂(b3)の数平均分子量は11000であった。
乾燥窒素気流下、TrisP-PA(商品名、本州化学工業(株)製)21.23g(0.05モル)と4-ナフトキノンジアジドスルホニル酸クロリド33.58g(0.125モル)を1,4-ジオキサン450gに溶解させ、室温にした。ここに、1,4-ジオキサン50gと混合させたトリエチルアミン12.65g(0.125モル)を反応系内が35℃以上にならないように滴下した。滴下後30℃で2時間攪拌した。トリエチルアミン塩を濾過し、ろ液を水に投入させた。その後、析出した沈殿をろ過で集めた。この沈殿を真空乾燥機で乾燥させ、ナフトキノンジアジド化合物(c2)を得た。このナフトキノンジアジド化合物のキノンジアジド置換率は83%であった。
乾燥窒素気流下、m-クレゾール108.0g(1.00モル)、37質量%ホルムアルデヒド水溶液75.5g(ホルムアルデヒド0.93モル)、シュウ酸二水和物0.63g(0.005モル)、メチルイソブチルケトン264gを仕込んだ後、油浴中に浸し、反応液を還流させながら、4時間重縮合反応を行った。その後、油浴の温度を3時間かけて昇温し、その後に、フラスコ内の圧力を4.0kPa~6.7kPaまで減圧し、揮発分を除去し、溶解している樹脂を室温まで冷却して、ノボラック型フェノール樹脂であるアルカリ可溶性樹脂(d1)を得た。GPCから重量平均分子量は3,500であった。
1000ccの4つ口フラスコにイソプロピルアルコールを100g仕込み、これをオイルバス中で80℃に保ち窒素シール、攪拌を行いながらメタクリル酸メチル30gとスチレン40g、メタクリル酸30gにN.N-アゾビスイソブチロニトリル2gを混合してこれを滴下ロートで30分かけて滴下した。この後、4時間反応を続けた後、ハイドロキノンモノメチルエーテルを1g添加してから常温に戻し重合を完了した。つぎにイソプロピルアルコールを100gを添加した後、これを75℃に保ちながらメタクリル酸グリシジル40gとトリエチルベンジルアンモニウムクロライド3gを添加し3時間反応させて、共重合体溶液を得た。続いて、共重合体溶液を室温まで冷却した後、共重合体溶液を水5Lに投入して白色沈殿を得た。この沈殿を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、目的のアクリル樹脂であるアルカリ可溶性樹脂(Ac-2)を得た。このアルカリ可溶性樹脂(Ac-2)の重量平均分子量は10000であった。
図1に、評価に使用する積層体の概略図を示す。
感光性樹脂組成物W3を用いて実施例1に記載の隔壁パターン4を形成した積層体Aを作成し、(4-3)樹脂硬化物表面と内部のXPS比較の評価を行った。感光性樹脂組成物W3の樹脂硬化物を樹脂硬化物W3と記載する。得られた樹脂硬化物W3表面のC1sスペクトル22と樹脂硬化物W3内部のC1sスペクトル23を図6に示す。
感光性樹脂組成物W10を用いて実施例1に記載の隔壁パターン4を形成した基板を作成し、(4-3)樹脂硬化物表面と内部のXPS比較の評価を行った。感光性樹脂組成物W10の樹脂硬化物を樹脂硬化物W10と記載する。得られた樹脂硬化物W10表面のC1sスペクトル24と樹脂硬化物W10内部のC1sスペクトル25を図7に示す。樹脂硬化物W10表面のC1sスペクトル24と樹脂硬化物W10内部C1sスペクトル25の比較で、CF2基由来のピークのピーク高さとCF3基由来のピークのピーク高さは同様であった。また、樹脂硬化物W10は、撥液性の評価が不良であった。
前記<FT-IRによる組成分析>に記載の方法で、感光性樹脂組成物W3(実施例8)、W7(比較例6)およびW8(比較例7)から形成した樹脂硬化物のIRスペクトルを測定した。感光性樹脂組成物W3とW7の樹脂硬化物のIRスペクトルより、1775~1780cm-1および1720~1725cm-1にイミド環構造中のカルボニル基伸縮振動に由来するピークが得られた。一方、感光性樹脂組成物W8の樹脂硬化物のIRスペクトルからは、イミド環構造の存在を閉めすスペクトルは見られなかった。
前記<熱分解GC/MSによる組成分析>に記載の方法で、感光性樹脂組成物W3(実施例9)およびW6(実施例10)の樹脂硬化物の熱分解物を分析した。分析の結果、感光性樹脂組成物W3の樹脂硬化物から、インデンに帰属されるピーク(450~455秒)が得られた。一方、感光性樹脂組成物W6の樹脂硬化物からは、インデンに帰属されるピークは見られなかった。
図1に、評価に使用する積層体の概略図を示す。
感光性樹脂組成物をW5に変更した以外は実施例11と同様に評価した。ハーフ露光で形成した樹脂硬化物W5(第2段)および、未露光で形成した樹脂硬化物W5(第1段)について、(4-1)樹脂硬化物表面のXPS分析を行い、得られたF原子とSi原子の元素濃度(atom%)を表3に示す。ハーフ露光で形成した樹脂硬化物W5(第2段)表面のC1sスペクトル27を図9に示す。また(5)耐久性の評価結果を表3に示す。
隔壁パターン12の作成方法を次のように変更した以外は実施例11と同様に評価した。
感光性樹脂組成物を表3に記載の種類に変更した以外は実施例13と同様に評価した。第1段および第2段の(4-1)樹脂硬化物表面のXPS分析を行い、得られたF原子とSi原子の元素濃度(atom%)を表3に示す。また、第2段である樹脂硬化物W10表面のC1sスペクトル29を図11に示す。また(5)耐久性の評価結果を表3に示す。
樹脂硬化物W10(第2段)表面のXPS分析結果は、特性(v)を満たす結果であった。樹脂硬化物W10(第2段)表面は親液性であり、(5)耐久性の評価で、図3に示すように、基板上にパターンニングされた第1電極8上および樹脂硬化物の第2段9上に機能性インク11を白抜けすることなく、連続して滴下することができた。
感光性樹脂組成物をW11に変更した以外は実施例11と同様に評価した。ハーフ露光で形成した樹脂硬化物W11(第2段)および、未露光で形成した樹脂硬化物W11(第1段)について、(4-1)樹脂硬化物表面のXPS分析を行い、得られたF原子とSi原子の元素濃度(atom%)を表3に示す。ハーフ露光で形成した樹脂硬化物W5(第2段)表面のC1sスペクトル31を図12に示す。また(5)耐久性の評価結果を表3に示す。
感光性樹脂組成物を表3に記載の種類に変更した以外は実施例13と同様に評価した。第1段および第2段の(4-1)樹脂硬化物表面のXPS分析を行い、得られたF原子とSi原子の元素濃度(atom%)を表3に示す。また、第2段である樹脂硬化物W10表面のC1sスペクトル32を図13に示す。また(5)耐久性の評価結果を表3に示す。
樹脂硬化物W10(第2段)表面のXPS分析結果は、特性(v)を満たす結果であった。樹脂硬化物W10(第2段)表面は親液性であり、(5)耐久性の評価で、図3に示すように、基板上にパターンニングされた第1電極8上および樹脂硬化物の第2段9上に機能性インク11を白抜けすることなく、連続して滴下することができた。
3 補助電極
4 隔壁パターン
5 隔壁パターン
6 有機EL層
7 第2電極
8 基板上にパターンニングされた第1電極
9 樹脂硬化物の第1段
10 樹脂硬化物の第2段
11 機能層
12 隔壁パターン
13 基板
14 平坦化層
16 樹脂硬化物
17 第1電極と樹脂硬化物が接する界面と反対側の表面
18 第1電極と前記樹脂硬化物が接する界面
19 第一電極と樹脂硬化物が接する界面に対して垂直、且つ前記基板から樹脂硬化物の方向であり、第一電極と樹脂硬化物が接する界面を起点に100~200nmの範囲
20 樹脂硬化物第1段の第1電極と樹脂硬化物が接する界面と反対側の表面
21 樹脂硬化物第2段の第1電極と樹脂硬化物が接する界面と反対側の表面
22 樹脂硬化物W3表面のC1sスペクトル
23 樹脂硬化物W3内部のC1sスペクトル
24 樹脂硬化物W10表面のC1sスペクトル
25 樹脂硬化物W10内部のC1sスペクトル
26 ハーフ露光で形成した樹脂硬化物W3(第2段)表面のC1sスペクトル
27 ハーフ露光で形成した樹脂硬化物W5(第2段)表面のC1sスペクトル
28 第2段である樹脂硬化物W10表面のC1sスペクトル
29 第2段である樹脂硬化物W10表面のC1sスペクトル
30 第一電極と樹脂硬化物が接する界面に対して垂直、且つ前記基板から樹脂硬化物の方向であり、第一電極と樹脂硬化物が接する界面を起点に100nm
31 ハーフ露光で形成した樹脂硬化物W5(第2段)表面のC1sスペクトル
32 第2段である樹脂硬化物W10表面のC1sスペクトル
Claims (10)
- 基板、該基板上にパターンニングされた第1電極、樹脂硬化物の順に積層され、前記第1電極上にある前記樹脂硬化物の少なくとも一部が開口している積層体であって、
X線光電子分光法(XPS)による前記樹脂硬化物の分析が特性(i)および特性(ii)を満たす積層体。
(i)前記第1電極と前記樹脂硬化物が接する界面と反対側の表面の少なくとも一部から測定される前記樹脂硬化物のF原子の濃度が8.1atom%以上30.0atom%以下、及び、Si原子の濃度が1.0atom%以上6.0atom%以下である
(ii)前記第1電極と前記樹脂硬化物が接する界面に対して垂直、且つ前記基板から前記樹脂硬化物の方向であり、前記第1電極と前記樹脂硬化物が接する界面を起点に100~200nmの範囲のいずれかで測定される前記樹脂硬化物のF原子の濃度が0.1atom%以上8.0atom%以下である - 前記特性(ii)におけるF原子の濃度が、4.0atom%以上7.5atom%以下である請求項1に記載の積層体。
- X線光電子分光法(XPS)による前記樹脂硬化物の分析において、
前記第1電極と前記樹脂硬化物が接する界面と反対側の表面の少なくとも一部から測定される前記樹脂硬化物のC1sスペクトル[A]と、
前記第1電極と前記樹脂硬化物が接する界面に対して垂直、且つ前記基板から樹脂硬化物の方向であり、前記第1電極と前記樹脂硬化物が接する界面を起点に100~200nmの範囲のいずれかで測定される前記樹脂硬化物のC1sスペクトル[B]が、
特性(iii)および特性(iv)を満たす請求項1または2に記載の積層体。
(iii)C1sスペクトル[B]における結合エネルギー290~292eVの範囲内にピークトップがあるCF2基由来のピークのピーク高さより、C1sスペクトル[A]における同ピーク高さの方が高い
(iv)C1sスペクトル[A]における結合エネルギー292~294eVの範囲内にピークトップがあるCF3基由来のピークのピーク高さより、C1sスペクトル[B]における同ピーク高さの方が高い - 前記樹脂硬化物がイミド環構造を有する化合物を含む請求項1~3のいずれかに記載の積層体。
- 前記樹脂硬化物がインデン構造を有する化合物を含む請求項1~4のいずれかに記載の積層体。
- 前記樹脂硬化物が、前記第1電極と前記樹脂硬化物が接する界面を起点とした厚さが0.8μm~10.0μmである第1段、および、前記第1電極と前記樹脂硬化物が接する界面を起点とした厚さが0.1μm~0.7μmである第2段を有する段差形状の樹脂硬化物であり、さらに、X線光電子分光法(XPS)による前記樹脂硬化物の分析において、前記樹脂硬化物の第1段が前記特性(i)を満たし、前記樹脂硬化物の第2段が特性(v)を満たす請求項1~5のいずれかに記載の積層体。
(v)前記第1電極と前記樹脂硬化物が接する界面と反対側の表面の少なくとも一部から測定されるF原子の濃度が0.1atom%以上20.0atom%以下、及び、Si原子の濃度が0.1atom%以上0.9atom%以下であり、且つ、C1sスペクトルにおける結合エネルギー290~295eVの範囲に測定される最大ピーク高さを持つピークが、292~294eVの範囲内にピークトップがあるCF3基由来のピークである - 前記特性(v)におけるF原子の濃度が、8.0atom%以上18.0atom%以下である請求項6に記載の積層体。
- 請求項1~7のいずれかに記載の積層体を具備する表示装置。
- 工程(5)および(6)をこの順に有する表示装置の製造方法。
(5)請求項1~7のいずれかに記載の積層体において、前記第1電極上に機能性インクをインクジェットで塗布して機能層を形成する工程
(6)該機能層上に第2電極を形成する工程 - 工程(7)および(8)をこの順に有する表示装置の製造方法。
(7)請求項6または7に記載の積層体において、前記第1電極上および前記樹脂硬化物の第2段上に機能性インクをインクジェットで塗布して機能層を形成する工程
(8)該機能層上に第2電極を形成する工程
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