WO2023013550A1 - 化合物、樹脂組成物、硬化物、及び表示装置 - Google Patents

化合物、樹脂組成物、硬化物、及び表示装置 Download PDF

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WO2023013550A1
WO2023013550A1 PCT/JP2022/029311 JP2022029311W WO2023013550A1 WO 2023013550 A1 WO2023013550 A1 WO 2023013550A1 JP 2022029311 W JP2022029311 W JP 2022029311W WO 2023013550 A1 WO2023013550 A1 WO 2023013550A1
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compound
resin composition
formula
carbon atoms
group
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French (fr)
Japanese (ja)
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西岡拓紀
小森悠佑
三好一登
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Toray Industries Inc
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Toray Industries Inc
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Priority to KR1020237039960A priority patent/KR20240045164A/ko
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/27—Compounds containing a nitrogen atom bound to two other nitrogen atoms, e.g. diazoamino-compounds
    • C08K5/28—Azides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • 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
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • G03F7/022—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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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 [2D] 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 [2D] radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • 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
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

Definitions

  • the present invention relates to a compound, a resin composition, a cured product using the same, and a display device.
  • Cured products obtained by curing compositions containing polyimide and polybenzoxazole are widely used as insulating films, protective films, and planarizing films for semiconductor devices and display devices.
  • a display device for example, in applications such as organic electroluminescence (Electroluminescence: hereinafter referred to as EL) display pixel division layer and liquid crystal display black matrix, the cured product is used to improve contrast. It is required to lower the light transmittance.
  • EL organic electroluminescence
  • TFT driving thin film transistor
  • carbon black, organic / inorganic pigments, dyes, etc. are added to the resin composition, as seen in black matrix materials for liquid crystal displays and RGB paste materials. and a method of adding a coloring agent.
  • Techniques for reducing the light transmittance of a cured product in a resin composition include, for example, a method of adding a quinonediazide compound to an alkali-soluble resin, a dye soluble in both an alkaline developer and an organic solvent (see Patent Document 1), A method of adding a black oil-soluble dye to a photosensitive resin (see Patent Document 2), and adding at least one colorant selected from an esterified quinonediazide compound and a dye, an inorganic pigment, and an organic pigment to an alkali-soluble heat-resistant resin. (see Patent Document 3), and a method of adding a xanthene-based acid dye and a triarylmethane-based acid dye to a binder resin (see Patent Document 4).
  • the present invention has the following configurations. [1] A compound represented by formula (1).
  • a n- is an n-valent anion represented by formula (2) or formula (3).
  • R 1 to R 4 each independently represent an alkyl group having 5 to 10 carbon atoms) where n is an integer from 1 to 3.
  • R 5 to R 8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
  • R 9 to R 14 are , each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R 15 to R 18 each independently represent a hydrogen atom, a halogen atom, —SO 3 H, —SO 3 ⁇ , —SO 3 NR 19 R 20 , —COOH, —COO — , —COOR 21 , —CONR 22 R 23 , —OR 24 , —NR 25 R 26 or optionally substituted carbon atoms 1 to 20 R 19 to R 26 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • R 5 At least one of R 8 and R 15 to R 18 is a monovalent hydrocarbon group having 1 to 10 carbon atoms having —SO 3 — or —COO
  • R 27 to R 30 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • R 31 to R 36 are Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms
  • R 37 to R 41 each independently represent a hydrogen atom, a halogen atom, —SO 3 H, —SO 3 — , —SO 3 NR 42 R 43 , -COOH, -COO - , -COOR 44 , -CONR 45 R 46 , -OR 47 , -NR 48 R 49 or 1 having 1 to 20 carbon atoms which may have a substituent represents a valent hydrocarbon group, adjacent ones among R 37 to R 41 may be bonded to each other to form a cyclic structure, and R 42 to R 49 each independently represent a hydrogen atom or represents an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein at least two of R 27
  • the quinonediazide compound contains a compound in which sulfonic acid of quinonediazide is ester-bonded to the hydroxy groups of the polyhydroxy compound, and 100 mol% of the hydroxy groups are ester-bonded to the sulfonic acid of quinonediazide.
  • thermochromogenic compound contains an aromatic hydrocarbon compound having at least one aromatic C—H bond and at least three phenolic hydroxyl groups in one aromatic ring, and further has the formula ( The resin composition according to [12] or [13] above, which contains a triazine ring-containing compound represented by 4).
  • R 50 to R 55 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms , a methylol group, and an alkoxymethyl group, provided that at least one of R 50 to R 55 is a methylol group or an alkoxymethyl group.
  • the (A) alkali-soluble resin contains one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof.
  • the resin composition according to any one of [14].
  • FIG. 1 is a schematic diagram of a substrate used in an organic EL display device
  • the compound of the present invention is a compound represented by formula (1).
  • the compound represented by formula (1) consists of an anion portion represented by A n- and a cation portion represented by (R 1 R 2 R 3 R 4 N + ) n .
  • a n- is an n-valent anion represented by formula (2) or formula (3).
  • R 5 to R 8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
  • R 9 to R 14 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms.
  • R 15 to R 18 each independently represent a hydrogen atom, a halogen atom, —SO 3 H, —SO 3 — , —SO 3 NR 19 R 20 , —COOH, —COO — , —COOR 21 , —CONR 22 R 23 , —OR 24 , —NR 25 R 26 or an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms;
  • R 19 to R 26 each independently represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • the optionally substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or the optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms has Substituents that may be used include halogen atoms, hydroxyl groups, alkoxy groups, phenoxy groups, carboxyl groups, sulfo groups, acyl groups, amino groups, imino groups, amide groups, imido groups, nitro groups, cyano groups, —SO 3 — , Known substituents such as —COO — can be mentioned.
  • R 5 to R 8 and R 15 to R 18 is a monovalent hydrocarbon group having 1 to 10 carbon atoms having —SO 3 — or —COO — , —SO 3 - or -COO - .
  • X represents -SO 3 - or -COO - .
  • R 27 to R 30 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • R 31 to R 36 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms.
  • R 37 to R 41 are each independently a hydrogen atom, a halogen atom, —SO 3 H, —SO 3 — , —SO 3 NR 42 R 43 , —COOH, —COO — , —COOR 44 , —CONR 45 R 46 , -OR 47 , -NR 48 R 49 or an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms; Adjacent ones among R 37 to R 41 may be bonded to each other to form a cyclic structure.
  • R 42 to R 49 each independently represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • mutually adjacent ones refer to groups existing at the ortho position of a substituent when a given group is focused on.
  • R 38 R 37 or R 39 corresponds to R 38 and R 38 adjacent to each other.
  • examples of the substituents that the monovalent hydrocarbon group having 1 to 20 carbon atoms that may have a substituent may have include the substituents described above.
  • At least two of R 27 to R 30 and R 37 to R 41 are monovalent hydrocarbon groups having 1 to 20 carbon atoms having -SO 3 - or -COO- , -SO 3 - or -COO- be. By satisfying this, the structure represented by Formula (3) becomes an anion.
  • R 1 to R 4 in the cation moiety are each independently an alkyl group having 5 to 10 carbon atoms. That is, the cation moiety is a quaternary ammonium cation having four alkyl groups each having 5 to 10 carbon atoms, each of which may be different. In formula (1), all of R 1 , R 2 , R 3 and R 4 are preferably the same substituent. That is, the cation moiety is preferably a quaternary ammonium cation having four identical alkyl groups of 5 to 10 carbon atoms.
  • R 1 to R 4 are the same substituent, it is possible to improve the reliability of an organic EL display device having, as a pixel dividing layer, a cured product made of a resin composition containing the compound of the present invention, which will be described later. can.
  • ammonium cations having four alkyl groups having 5 to 10 carbon atoms include tetrapentylammonium cations, tetrahexylammonium cations, tetraoctylammonium cations, tetradecylammonium cations, and the like.
  • R 1 , R 2 , R 3 and R 4 in formula (1) are preferably alkyl groups having 5 or 6 carbon atoms, such as tetrapentylammonium cation (5 carbon atoms), tetrahexylammonium It preferably has a cation (6 carbon atoms) structure.
  • the compound represented by formula (1) is, for example, an aqueous solution of a salt containing an anion represented by formula (2) or formula (3) (hereinafter referred to as an anion component) and a salt containing the quaternary ammonium cation (by preparing aqueous solutions of each component (hereinafter referred to as a cation component) and mixing the two with stirring, the compound is produced as a precipitate.
  • the counter cation contained in the anion component is not particularly limited, and examples thereof include sodium cations and potassium cations.
  • the counter anion contained in the cation component is not particularly limited, and examples thereof include chloride anions and bromide anions.
  • the compound represented by the formula (1) can be obtained by collecting the generated precipitate by filtration.
  • the obtained compound represented by formula (1) is preferably dried at about 60 to 70°C.
  • a compound represented by formula (1) can be identified by a known method.
  • the hydrogen nuclear magnetic resonance ( 1 H NMR) spectrum of the compound represented by Formula (1) is a superposition of peaks derived from anions and cations that constitute the compound. These peaks can be distinguished by comparing the 1H NMR spectra of the anionic and cationic components, respectively.
  • the triplet peak derived from the alkyl terminal (CH 3 ) of the quaternary ammonium cation having four alkyl groups with 5 to 10 carbon atoms appears in the chemical shift value ( ⁇ ) region of 0.5 to 1.0. .
  • the peak becomes a single triplet peak and the integrated value is 12 ⁇ n.
  • the compound of the present invention preferably has a maximum absorption wavelength in the range of 350 nm or more and 700 nm or less in any of the range of 500 nm or more and 700 nm or less.
  • the maximum absorption wavelength of the compound of the present invention is within this range, the sensitivity of the photosensitive resin composition containing the compound of the present invention, which will be described later, can be improved.
  • the resin composition of the present invention contains the compound of the present invention and (A) an alkali-soluble resin.
  • the content of the compound represented by formula (1) in the resin composition is preferably 10 to 75 parts by mass, more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A).
  • the content of the compound represented by Formula (1) is 10 parts by mass or more, the light of the corresponding wavelength can be sufficiently absorbed. Further, by setting the amount to 75 parts by mass or less, it is possible to reduce the residue at the opening.
  • the mass ratio of the ammonium cation species in the formula (1) to the total mass of the organic cation species is preferably 50% by mass or more and 100% by mass or less.
  • the mass ratio of the ammonium cation species is within this range, the storage stability of the resin composition of the present invention during frozen storage can be enhanced.
  • the total mass of organic cationic species and the percentage mass of ammonium cationic species can be determined by cation chromatography.
  • the compound represented by formula (1) is a compound having a maximum absorption wavelength in the range of 500 nm or more and less than 580 nm in the range of 350 nm or more and 700 nm or less, and a compound having a maximum absorption wavelength in the range of 350 nm or more and 700 nm or less. It is preferable to contain a compound having a maximum absorption wavelength in the range of 580 nm or more and 700 nm or less. By containing these compounds, the transmittance of the cured product can be reduced over a wide range of the visible light region. Furthermore, if necessary, the cured product can be made black by using (C) a thermochromic compound described later in combination.
  • Examples of compounds represented by formula (1) having a maximum absorption wavelength in the range of 500 nm or more and less than 580 nm in the region of 350 nm or more and 700 nm or less include C.I. I. Compounds having an anion moiety of Acid Red 52,289 and the like can be mentioned. Examples of the compound represented by formula (1) having a maximum absorption wavelength in the range of 580 nm to 700 nm in the range of 350 nm to 700 nm include C.I. I. Compounds having an anion portion of Acid Blue 83 and 90 are included.
  • the total mass of all chlorine atoms and all bromine atoms contained in the resin composition is preferably 150 mass ppm or less with respect to the total mass of solids in the resin composition. , 100 ppm by mass or less, and more preferably less than 2 ppm by mass, which is the detection limit of combustion ion chromatography.
  • the total mass of all chlorine atoms and all bromine atoms contained in the resin composition can be determined, for example, by burning the resin composition in a combustion tube of an analyzer, absorbing the generated gas into a solution, and subjecting a part of the absorption liquid to ion chromatography. It can be determined by combustion ion chromatography with graphical analysis.
  • the resin composition of the present invention contains (A) an alkali-soluble resin.
  • An alkali-soluble resin is a resin having a dissolution rate of 50 nm/min or more as defined below. More specifically, a silicon wafer is coated with a solution obtained by dissolving a resin in ⁇ -butyrolactone, and prebaked at 120° C. for 4 minutes to form a prebaked film having a film thickness of 10 ⁇ m ⁇ 0.5 ⁇ m.
  • a resin having a dissolution rate of 50 nm/min or more which is obtained from the film thickness reduction when immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 1° C. for 1 minute and then rinsed with pure water.
  • the alkali-soluble resin preferably has an acidic group in the structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility.
  • Preferred acidic groups include carboxyl groups, hydroxyl groups, sulfonic acid groups, and thiol groups.
  • alkali-soluble resins include polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, phenolic resins, polymers composed of radically polymerizable monomers having alkali-soluble groups, siloxane polymers, and cyclic olefins. Polymers, cardo resins, and the like.
  • the alkali-soluble resin may contain two or more of these resins.
  • Alkali-soluble resin preferably contains one having high heat resistance.
  • the alkali-soluble resin has a temperature of 200° C. or higher after heat treatment. It is preferable to contain a material with a small amount of outgassing at a high temperature of .
  • the alkali-soluble resin preferably contains one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof. .
  • Polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and their copolymers will be explained.
  • Polyimide is not particularly limited as long as it has an imide ring
  • polybenzoxazole is not particularly limited as long as it has a benzoxazole ring.
  • the polyimide precursor is not particularly limited as long as it has a structure that becomes a polyimide having an imide ring by dehydration and ring closure. It is not particularly limited as long as it has a structure that becomes oxazole.
  • Polyimides, polyimide precursors, polybenzoxazoles, and polybenzoxazole precursors are more preferably used as the alkali-soluble resin.
  • a polyimide has a structural unit represented by formula (5).
  • R 56 represents a 4- to 10-valent organic group
  • R 57 represents a 2- to 10-valent organic group
  • R 58 and R 59 each independently represent a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group, or a substituent represented by formula (6) or formula (7).
  • p represents an integer of 0 to 6
  • q represents an integer of 0 to 8, and p+q>0.
  • R 60 to R 62 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or represents an aryl group.
  • the above alkyl group, acyl group and aryl group may be unsubstituted or substituted.
  • a polyimide precursor has a structural unit represented by formula (8).
  • R 63 represents a 4- to 10-valent organic group
  • R 64 represents a 2- to 10-valent organic group
  • R 65 represents a substituent represented by the formula (6) or formula (7)
  • R 66 represents a hydroxyl group, a sulfonic acid group, or a thiol group
  • R 67 represents a hydroxyl group, a sulfonic acid group, a thiol group, or the formula ( 6) or a substituent represented by formula (7)
  • r represents an integer of 2 to 8
  • s represents an integer of 0 to 6
  • t represents an integer of 0 to 8, and 2 ⁇ r+s ⁇ 8.
  • Polybenzoxazole has a structural unit represented by formula (9).
  • R 68 represents a divalent to 10-valent organic group
  • R 69 represents a 4- to 10-valent organic group having an aromatic structure
  • R 70 and R 71 each independently represent a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group, or a substituent represented by formula (6) or formula (7).
  • u represents an integer from 0 to 8
  • v represents an integer from 0 to 6, and u+v>0.
  • a polybenzoxazole precursor has a structural unit represented by formula (10).
  • R 72 represents a divalent to 10-valent organic group having an aromatic structure
  • R 73 represents a 4- to 10-valent organic group
  • R 74 represents a sulfonic acid group, a thiol group or a substituent represented by formula (6) or formula (7)
  • R 75 represents a hydroxyl group, carboxy group, sulfonic acid group, thiol group or formula (6) or formula ( represents a substituent represented by 7);
  • w represents an integer of 2 to 8
  • x represents an integer of 0 to 8
  • y represents an integer of 0 to 6, and 2 ⁇ w+y ⁇ 8.
  • At least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof is the above formula (5), formula (8), formula (9) or formula It preferably has 5 to 100,000 structural units represented by (10). Further, one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof is the above formula (5), formula (8), formula (9) Alternatively, it may have other structural units in addition to the structural units represented by formula (10).
  • At least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof is the above formula (5), formula (8), formula (9) ) or formula (10) in an amount of 50 mol % or more, more preferably 70 mol % or more of the total number of structural units.
  • R 56 -(R 58 ) p in formula (5) and (R 65 ) r -R 63 -(R 66 ) s in formula (8) are residues of tetracarboxylic acid or derivatives thereof. show. Residues of tetracarboxylic acid derivatives include residues of tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid active diesters.
  • residues of tetracarboxylic acids or derivatives thereof include pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid.
  • R 76 represents an oxygen atom, C(CF 3 ) 2 or C(CH 3 ) 2 .
  • R77 and R78 each independently represent a hydrogen atom or a hydroxyl group.
  • R 68 -(R 70 ) u in the formula (9) and R 72 -(R 74 ) x in the formula (10) each represent a residue of a dicarboxylic acid or a derivative thereof.
  • Residues of dicarboxylic acid derivatives include residues of dicarboxylic anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.
  • dicarboxylic acid residues or residues of derivatives thereof examples include terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, etc., or , their dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, and the like.
  • tricarboxylic acid residues or residues of derivatives thereof include trimellitic acid, trimesic acid, diphenylethertricarboxylic acid, biphenyltricarboxylic acid, etc., or tricarboxylic acid anhydrides, tricarboxylic acid chlorides, and tricarboxylic acids thereof. Examples include residues such as active esters.
  • R 57 -(R 59 ) q in formula (5) and R 64 -(R 67 ) t in formula (8) represent a residue of diamine or a derivative thereof.
  • R 69 -(R 71 ) v in formula (9) and (OH) w -R 73 -(R 75 ) y in formula (10) are bisaminophenol compounds or derivative residues thereof among diamines. represents Diamine and bisaminophenol derivatives include diisocyanate compounds or trimethylsilylated diamines.
  • residues of diamines and bisaminophenol compounds or residues of derivatives thereof include 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diamino diphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethyl-4,4
  • R 76 represents an oxygen atom, C(CF 3 ) 2 or C(CH 3 ) 2 .
  • R 77 to R 80 each independently represent a hydrogen atom or a hydroxyl group.
  • alkali-soluble resins by blocking the terminal of these alkali-soluble resins with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having an acidic group, an alkali-soluble resin having an acidic group at the main chain terminal can be obtained.
  • Preferred examples of such monoamines having an acidic group include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino -4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. You may use 2 or more types of these.
  • acid anhydrides, acid chlorides and monocarboxylic acids include acids such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride and 3-hydroxyphthalic anhydride.
  • Monocarboxylic acids such as anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, monoacid chloride compounds in which the carboxyl groups of these are acid chlorides, monoacid chloride compounds and N -hydroxybenzotriazole and active ester compounds obtained by reaction with N-hydroxy-5-norbornene-2,3-dicarboximide. You may use 2 or more types of these.
  • the (A) alkali-soluble resin used in the resin composition is synthesized by a known method.
  • the production methods include, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, and a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol.
  • polyimide it can be obtained, for example, by subjecting the polyamic acid or polyamic acid ester obtained by the method described above to dehydration and ring closure by heating or chemical treatment with an acid or base.
  • a polybenzoxazole precursor such as polyhydroxyamide
  • it can be obtained by a condensation reaction between a bisaminophenol compound and a dicarboxylic acid.
  • a solution of dichloride is added dropwise.
  • polybenzoxazole it can be obtained, for example, by dehydrating and ring-closing the polyhydroxyamide or the like obtained by the above-described method by heating or chemical treatment with an acid or base.
  • the content of the alkali-soluble resin is the resin composition 100 from the viewpoint of obtaining excellent properties as planarizing films, pixel dividing layers, partition walls, and protective films used in organic light-emitting devices, display devices, and semiconductor elements. It is preferably contained in an amount of 0.5% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less.
  • the resin composition of the present invention preferably further contains (B) a photosensitive compound.
  • a photosensitive compound By containing a photosensitive compound, the resin composition can be made into a photosensitive resin composition and patterned by photolithography.
  • Photosensitive compounds include photoacid generators and photopolymerization initiators. From the viewpoint of resolution, the photosensitive compound preferably contains a photoacid generator.
  • a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, an iodonium salt, and the like can be contained as the photoacid generator.
  • the photosensitive compound preferably contains a quinonediazide compound.
  • the quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is sulfonamide-bonded, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and/or sulfonamide. and the like.
  • the quinonediazide compound contains a compound in which the sulfonic acid of quinonediazide is ester-bonded to the hydroxy groups of the polyhydroxy compound, and the sulfonic acid of quinonediazide is It is more preferable that the ratio of hydroxy groups ester-bonded with is 50 mol % or more and 90 mol % or less.
  • the affinity of the quinonediazide compound to an alkaline aqueous solution is reduced, and the solubility of the unexposed area of the resin composition in an alkaline aqueous solution is greatly reduced.
  • the sulfonyl group is changed to indenecarboxylic acid, and a high dissolution rate in an alkaline aqueous solution of the resin composition in the exposed area can be obtained.
  • a pattern can be obtained with resolution.
  • the quinonediazide compound substituted by 90 mol % or less it is possible to suppress the residue in the pattern openings.
  • a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm) and g-line (436 nm) of a general mercury lamp.
  • the photoacid generators may be used alone or in combination of two or more, and a highly sensitive photosensitive resin composition can be obtained.
  • both a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group are preferably used.
  • a 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure and full-wavelength exposure.
  • a 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength.
  • a naphthoquinonediazidesulfonyl ester compound can be obtained by using a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule together, or a 4-naphthoquinonediazidesulfonyl ester compound and a 5-naphthoquinonediazidesulfonyl ester compound. can also be used together.
  • the molecular weight of the photoacid generator is preferably 300 or more, more preferably 350 or more, preferably 3000 or less, more preferably 1500 or less, from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the cured product obtained by heat treatment. is.
  • the content of the photosensitive compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 100 parts by mass or less, more preferably with respect to 100 parts by mass of the alkali-soluble resin (A). is 80 parts by mass or less. If it is 1 to 100 parts by mass, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the cured product after heat treatment.
  • the resin composition of the present invention preferably further contains (C) a thermochromic compound.
  • the thermochromic compound does not have a maximum absorption wavelength in the region of 350 nm or more and 700 nm or less before heating, and generates a maximum absorption wavelength in any of the regions of 350 nm or more and 700 nm or less by heating at 120 ° C. or more (hereinafter , sometimes referred to as “thermocoloring”).
  • the thermochromogenic compound preferably contains a compound that, when heated at 120° C. or higher, produces a maximum absorption wavelength in any of the regions of 350 nm to 700 nm and 350 nm to 500 nm.
  • thermochromic compound is preferably a thermochromic compound that thermally develops color at a temperature higher than 180°C.
  • the higher the temperature at which the thermochromic compound thermally develops color the better the heat resistance under high temperature conditions, and the less the color fades due to prolonged irradiation with ultraviolet light and visible light, and the better the light resistance.
  • thermochromogenic compound may be a general heat-sensitive dye or pressure-sensitive dye, or may be another compound.
  • thermochromic compounds are those that develop color by changing their chemical structure and charge state due to the action of acidic groups coexisting in the system during heat treatment at 120 ° C. or higher, or those that develop color by the presence of oxygen in the air. Examples include those that cause a thermal oxidation reaction or the like to develop a thermal color.
  • thermochromic compound examples include a triarylmethane skeleton, a diarylmethane skeleton, a fluorane skeleton, a bislactone skeleton, a phthalide skeleton, a xanthene skeleton, a rhodamine lactam skeleton, a fluorene skeleton, a phenothiazine skeleton, a phenoxazine skeleton, and a spiropyran skeleton. be done.
  • Specific examples include the compounds described in JP-A-2004-326094. Among them, a hydroxyl group-containing compound having a triarylmethane skeleton is particularly preferable because of its high heat color development temperature and excellent heat resistance. These may be contained singly or in combination.
  • thermochromogenic compound contains an aromatic hydrocarbon compound having at least one aromatic C—H bond and at least three phenolic hydroxyl groups in one aromatic ring, and further, the formula (4) It is also preferable to contain a triazine ring-containing compound represented by.
  • R 50 to R 55 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, It represents a methylol group and an alkoxymethyl group having 2 to 10 carbon atoms. At least one of R 50 to R 55 is a methylol group or an alkoxymethyl group having 2 to 10 carbon atoms.
  • Aromatic hydrocarbons having at least one aromatic C—H bond and three phenolic hydroxyl groups in one aromatic ring include, for example, phloroglucinol, pyrogallol, 1,2.4-trihydroxybenzene, 2,4 ,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, galacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate , propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone and the like.
  • aromatic hydrocarbons having at least one aromatic C—H bond and four or more phenolic hydroxyl groups in one aromatic ring include 1,2,3,4-tetrahydroxybenzene, 1,2, 3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, leucoquinizarin and the like.
  • at least one substitution position of the other phenolic hydroxyl group for one of the phenolic hydroxyl groups is preferably the ortho or para position.
  • the Examples of the compound in which at least one substitution position of the other phenolic hydroxyl group with respect to any phenolic hydroxyl group is at the para position include 1,2.4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 1, 2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, leucoquinizarin and the like.
  • R 50 to R 55 has a methylol group or an alkoxymethyl group, and are preferably two or more, more preferably three or more, even more preferably four or more, and most preferably all six are methylol groups or alkoxymethyl groups.
  • Alkoxymethyl groups include methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl groups.
  • the content of (C) the thermochromic compound used in the present invention is preferably 5 to 80 parts by mass, particularly preferably 10 to 60 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin.
  • the content of (C) the thermochromic compound is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet-visible region can be reduced. Moreover, if it is 80 parts by mass or less, the heat resistance and strength of the cured product can be maintained, and the water absorption can be reduced.
  • the resin composition of the present invention may contain other colorants.
  • coloring agents include dyes, organic pigments, and inorganic pigments, and can be used according to the purpose.
  • the resin composition of the present invention includes a compound represented by formula (1), (A) an alkali-soluble resin, (B) a photosensitive compound, (C) a thermochromic compound, and other compounds other than colorants, such as heat Various known additives such as a cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver and a surfactant may be contained.
  • the resin composition of the present invention may contain a solvent.
  • Solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 - polar aprotic solvents such as imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyamide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene ethers such as glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl
  • the content of the solvent is preferably 100 parts by mass or more in order to dissolve the composition in 100 parts by mass of the alkali-soluble resin (A). Moreover, the content of the solvent is preferably 10000 parts by mass or less, more preferably 5000 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin, from the viewpoint of coating properties.
  • the resin composition of the present invention can be used for forming insulating films, protective films, flattening films, etc. of semiconductor elements and display devices. Among them, it is preferably used for forming a planarizing layer and a pixel dividing layer of an organic EL display device because it is excellent in high heat resistance and low outgassing property to a planarizing layer and a pixel dividing layer. From the point of view of improving the contrast, it is particularly preferable to be used for forming the pixel division layer of the organic EL display device.
  • a compound represented by formula (1) (A) an alkali-soluble resin, optionally (B) a photosensitive compound, (C) a thermochromic compound, and other coloring agents, which are components constituting the resin composition of the present invention. , a thermal cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver, a surfactant, a solvent, etc., to obtain a resin composition.
  • the resin composition to be used in the method for producing a resin composition film of the present invention which will be described later, contains a solvent to dissolve the respective components. In such a case, methods for promoting dissolution include heating and stirring.
  • the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually room temperature to 80°C. In this specification, room temperature is 25°C.
  • the order of dissolving each component is not particularly limited, and for example, a method of sequentially dissolving a compound having a low solubility in a solvent may be used.
  • the rotation speed is preferably set within a range that does not impair the performance of the resin composition, and is usually 200 rpm to 2000 rpm. Even when the mixture is stirred, it may be heated as necessary, and the temperature is usually from room temperature to 80°C.
  • ingredients that tend to generate air bubbles during stirring and dissolution such as surfactants and some adhesion improvers
  • dissolving the other ingredients before adding them at the end will prevent poor dissolution of other ingredients due to air bubbles. can be prevented.
  • the obtained resin composition is preferably filtered using a filtration filter to remove dust and particles.
  • filter pore sizes include, but are not limited to, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.05 ⁇ m, and 0.02 ⁇ m.
  • Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred.
  • PP polypropylene
  • PE polyethylene
  • nylon NY
  • PTFE polytetrafluoroethylene
  • polyethylene and nylon are preferred.
  • a first aspect of the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
  • a second aspect of the cured product of the present invention is a cured product containing the compound of the present invention.
  • the cured product of the present invention can be obtained, for example, by coating a substrate or the like with a resin composition containing the compound represented by the above formula (1), followed by heat treatment and curing.
  • the heat treatment conditions are preferably 200° C. or higher, more preferably 250° C. or higher.
  • the heat treatment conditions are preferably 400° C. or lower, more preferably 350° C. or lower.
  • (1) the above-described resin composition is applied to a substrate to form a coating film, (2) the coating film is exposed to actinic radiation, and the exposed coating (3) developing the exposed coating film with an alkaline solution to obtain a developed coating film; and (4) heating the developed coating film to obtain a cured product. have in this order.
  • the resin composition of the present invention is applied by, for example, a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc., and the resin composition is coated. Get a coating of things.
  • the substrate to be coated with the 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.
  • a method of treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, vapor treatment, and the like.
  • the formed coating film is optionally dried under reduced pressure, and then using a hot plate, oven, infrared rays, etc., in the range of 50 ° C. to 180 ° C. for 1 minute to several hours.
  • a coating film is obtained by applying the heat treatment of.
  • the coating film is irradiated with actinic radiation (hereinafter sometimes referred to as exposure). At this time, if necessary, the exposure may be performed through a photomask having a desired pattern, or the coating film may be exposed directly with a laser or the like.
  • Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc. In the present invention, i-rays (365 nm), h-rays (405 nm) and g-rays (436 nm) of mercury lamps can be used. preferable.
  • the exposed coating film is developed using an alkaline solution to remove the exposed portion of the coating film.
  • the developer at this time is tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol. , dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and other alkaline compounds.
  • 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,
  • 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.
  • 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.
  • the step of heat-treating the developed coating film to obtain a cured product By heat-treating the developed coating film, the residual solvent and components with low heat resistance can be removed, so that the heat resistance and chemical resistance of the cured product can be improved.
  • a certain 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.
  • a method of heat-treating at 230° C. for 60 minutes can be used.
  • the heat treatment conditions in the present invention are preferably 200° C. or higher, more preferably 230° C. or higher.
  • the heat treatment conditions are preferably 400° C. or lower, more preferably 350° C. or lower.
  • the display device of the present invention comprises the cured product of the present invention.
  • a cured product obtained by curing the resin composition is a substrate on which TFTs are formed, a flattening layer on the driving circuit, a pixel dividing layer and a display element on the first electrode, and a flattening layer of a display device having the second electrode in this order. and the pixel division layer.
  • Examples of display devices having such a configuration include liquid crystal display devices and organic EL display devices.
  • the pixel division layer is particularly suitable for use in organic EL display devices in which high heat resistance and low outgassing properties are required for the planarization layer and the pixel division layer, and can improve the contrast of the organic EL display device. is particularly preferably used for
  • a cured product obtained by curing the resin composition of the present invention may be used for either one of the flattening layer and the pixel dividing layer, or may be used for both.
  • An active matrix type display device has a TFT and wirings located on the sides of the TFT and connected to the TFT on a substrate such as glass, and has a flattening layer thereon so as to cover unevenness. Furthermore, 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.
  • the resin compositions prepared in Examples and Comparative Examples were spun onto a glass substrate (manufactured by Geomatec Co., Ltd.; hereinafter referred to as "ITO substrate") on which an ITO film was formed by sputtering. It was applied by spin coating using a coater (MS-A100; manufactured by Mikasa) so that the film thickness after heat treatment (cure) was 3.0 ⁇ m, and a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE) was used. was prebaked at 120° C. for 120 seconds to prepare a prebaked film. The resulting prebaked film was developed with a 2.38% by mass tetramethylammonium (TMAH) aqueous solution for 60 seconds to obtain a desired film thickness, and then rinsed with pure water to obtain a developed film.
  • TMAH mass tetramethylammonium
  • the film thicknesses of the pre-baked film and the developed film at the center of the substrate are measured using a stylus profiler (P-15; manufactured by KLA-Tencor Co., Ltd.). determined as follows.
  • Remaining film ratio [%] (film thickness of developed film)/(film thickness of prebaked film) x 100
  • C Remaining film rate is less than 50%.
  • Aperture dimension change [ ⁇ m] (aperture dimension after development) - (aperture dimension after curing)
  • FIGS. 1(a) Schematic diagrams of the substrates used are shown in FIGS.
  • an ITO transparent conductive film of 10 nm was formed on the entire surface of the substrate by a sputtering method and etched as a first electrode 2 .
  • an auxiliary electrode 3 was also formed in order to take out the second electrode (FIG. 1(a)).
  • the obtained substrate was ultrasonically cleaned for 10 minutes with "Semicoclean" (registered trademark) 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then cleaned with ultrapure water.
  • the entire surface of the substrate was coated with the photosensitive resin composition prepared in each example and comparative example by spin coating, and prebaked on a hot plate at 100° C. for 2 minutes.
  • the film was exposed to UV light through a photomask, it was developed with a 2.38 mass % tetramethylammonium hydroxide aqueous solution to dissolve only the exposed portion, and then rinsed with pure water.
  • the resulting pattern was cured in an oven at 230° C. for 60 minutes under a nitrogen atmosphere.
  • the pixel division layer 4 having a width of 70 ⁇ m and a length of 260 ⁇ m is arranged at a pitch of 155 ⁇ m in the width direction and a pitch of 465 ⁇ m in the length direction, and each opening exposes the first electrode. It is formed only in the effective area of the substrate (FIG. 1(b)). Note that this opening finally becomes a light-emitting pixel.
  • the effective area of the substrate was 16 mm square, and the thickness of the insulating layer was about 1.0 ⁇ m.
  • an organic EL display device was produced using the substrate on which the first electrode 2, the auxiliary electrode 3 and the pixel dividing layer 4 were formed.
  • an organic EL layer 5 including a light-emitting layer was formed by a vacuum deposition method (FIG. 1(c)).
  • the degree of vacuum during vapor deposition was 1 ⁇ 10 ⁇ 3 Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition.
  • 10 nm of compound (HT-1) was deposited as a hole injection layer
  • 50 nm of compound (HT-2) was deposited as a hole transport layer.
  • a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm with a doping concentration of 10%.
  • compounds (ET-1) and (LiQ) as electron-transporting materials were laminated at a volume ratio of 1:1 to a thickness of 40 nm. Structures of compounds used in the organic EL layer are shown below.
  • the film thickness referred to here is the value displayed by the crystal oscillation type film thickness monitor.
  • the produced organic EL display device was driven to emit light by direct current driving at 10 mA/cm 2 , and the light emitting area in the light emitting pixel (light emitting area before UV light irradiation) was measured. Next, it was placed on a hot plate heated to 80° C. with the light-emitting surface facing up, and irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 mW/cm 2 . After 1000 hours, light was emitted by direct current driving at 10 mA/cm 2 , and the light-emitting area in the light-emitting pixel (light-emitting area after UV light irradiation) was measured.
  • Luminescent area ratio [%] (luminous area after UV light irradiation) / (luminous area before UV light irradiation) x 100
  • the measurement area was about 201 cm 2 inside a circle with a radius of 8 cm from the center of the wafer, and the number of foreign substances (defect density) per 1 cm 2 of the coating film was determined. "A” when the defect density per substrate is less than 1.00/cm 2 , "B” when it is 1.00/cm 2 or more and less than 3.00/cm 2 , When it was 3.00/cm 2 or more, it was judged as "C".
  • Table 1 shows the anion components and cation components used in Synthesis Examples 1-11.
  • HA hydroxy group-containing diamine compound
  • Example 1 Under yellow light, the compound z-1 obtained in Synthesis Example 1 as the compound represented by formula (1), (A) the polyimide precursor resin a-1 obtained in Synthesis Example 12 as an alkali-soluble resin, (B) photosensitive compound b-1 obtained in Synthesis Example 13 as a chemical compound, compound c-1 as a thermochromic compound (C), thermal cross-linking agent d-1 as other additives, ⁇ -butyrolactone (GBL) and ethyl lactate as a solvent ( EL) was added in the amount shown in Table 1 and dissolved by stirring to prepare composition 1.
  • composition 1 we evaluated the residual film ratio, change in opening size, and reliability.
  • Examples 2 to 11 Comparative Examples 1 to 3
  • Compositions 2 to 14 were prepared according to the compositions shown in Table 2 in the same manner as in Example 1.
  • Compositions 2-14 were evaluated in the same manner as in Example 1.
  • compositions 1 and 11 were evaluated for frozen storage stability.
  • Tables 2 and 3 show the compositions and evaluation results of the resin compositions of Examples and Comparative Examples.
  • compositions 12 to 14 which did not contain the compound represented by formula (1), had a low residual film rate. It was confirmed that the resin composition containing the compound represented by the formula (1) of the present invention has a high residual film rate.
  • the compound, resin composition, and cured product of the present invention can be used as a surface protective film of a semiconductor device, an interlayer insulating film, a pixel division layer of an organic EEL device, a flattening film of a driving TFT substrate of a display device using an organic EL device, It is suitably used for wiring protective insulating films for circuit boards, on-chip microlenses for solid-state imaging devices, flattening films for various displays and solid-state imaging devices, and solder resists for circuit boards.

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