Hardened film and organic el display device

Abstract

[Problem] To provide a cured film which has excellent long-term reliability and which, in particular, is capable of suppressing a decrease in luminance during high-temperature continuous driving when used in an organic EL display device. [Solution] A cured film according to the present invention contains a polyimide and / or a polybenzoxazole, and the molar ratio F (fluorine atom) / C (carbon atom) of fluorine atoms to carbon atoms obtained when a cross-section of the cured film is measured using an electron probe microanalyzer is 0-0.05 (inclusive).

Description

Technical Field

[0001] This invention relates to a hardened film and an organic EL display device using the same. Background Technology

[0002] In display devices with thin displays, such as smartphones, tablet computers (PCs), and televisions, many products using organic electroluminescence (hereinafter, "organic EL") display devices have been developed.

[0003] Generally, organic EL display devices have a driving circuit, a planarization layer, a first electrode, a pixel segmentation layer, an organic EL layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes or by flowing current. Among these, a hardened film of a photosensitive resin composition that can be patterned by ultraviolet light is generally used as the material for the planarization layer and the pixel segmentation layer.

[0004] On the other hand, the requirements for high reliability of organic EL display devices are becoming increasingly stringent year by year. For materials used in planarization layers and pixel segmentation layers, it is required that they do not exhibit a decrease in luminous brightness or pixel shrinkage after reliability tests under accelerated conditions such as high temperature, high humidity, light irradiation, and continuous driving. Pixel shrinkage here refers to the phenomenon of reduced luminous brightness or failure to light up at the ends of pixels.

[0005] Examples of curing films based on positive photosensitive resin compositions proposed to date include: curing films using a composition in which a photosensitive component, naphthoquinone diazidosulfonate compound, is mixed in an alkali-soluble resin; curing films using a polyimide precursor as the resin before curing (see, for example, Patent Document 1); and curing films using a polybenzoxazole precursor as the resin before curing (see, for example, Patent Document 2).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2002-91343

[0009] Patent Document 2: Japanese Patent Application Publication No. 2002-116715

[0010] Patent Document 3: International Publication No. 2016-047483 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, the materials proposed in the listed patent documents cannot be said to have sufficient performance from the viewpoint of long-term reliability. On the other hand, as a material for the pixel division layer of an organic EL display device, a positive photosensitive resin composition has been proposed that improves long-term reliability by setting the sulfur concentration in the hardened film within a certain range (see, for example, Patent Document 3). However, while the hardened film containing the resin composition described in Patent Document 3 improves long-term reliability against light irradiation, it cannot be said to sufficiently suppress the decrease in luminance during continuous high-temperature operation. In view of the aforementioned problems, the present invention aims to provide a hardened film with excellent long-term reliability, particularly for use in an organic EL display device, which suppresses the decrease in luminance during continuous high-temperature operation.

[0013] Technical means to solve the problem

[0014] To solve the aforementioned problem, the hardened film of the present invention has the following structure.

[0015] [1] A hardening film comprising polyimide and / or polybenzoxazole, wherein the hardening film contains...

[0016] When the profile of the hardened film was measured using an electron probe microanalyzer, the molar ratio of fluorine atoms to carbon atoms, F (fluorine atoms) / C (carbon atoms), was greater than 0 and less than 0.05.

[0017] [2] The hardened membrane according to [1] further contains one or more compounds selected from the group consisting of carboxylic acids containing an indene structure, carboxylic acid esters containing an indene structure, sulfonic acids containing an indene structure, and aryl sulfonates containing an indene structure.

[0018] [3] The hardened film according to [1] or [2] also has polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer.

[0019] [4] The hardened membrane according to any one of [1] to [3] further comprises an aromatic hydrocarbon compound having at least three phenolic hydroxyl groups in an aromatic ring.

[0020] [5] The hardened film according to any one of [1] to [4] further contains β-alkoxypropionamide.

[0021] [6] The hardened membrane according to any one of [1] to [5] further comprises one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5), or a sulfonate ion derived from one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5):

[0022] [Chemistry 1]

[0023]

[0024] In equation (3), R 5 Each of the following independently represents a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, where n represents an integer from 1 to 5; in equation (4), R 6 A monovalent organic group representing 1 to 10 carbon atoms.

[0025] [7] The hardened film according to any one of [1] to [6], wherein the polyimide and / or polybenzoxazole has repeating units comprising an acid component and an amine component,

[0026] With the acid and amine components in all repeating units set to 100 mol%, the total of acid components with fluorene structures and amine components with fluorene structures in the total of 200 mol% is between 0 mol% and 50 mol%.

[0027] [8] The hardened membrane according to any one of [1] to [7], wherein the polyimide and / or polybenzoxazole has residues represented by formula (6):

[0028] [Chemistry 2]

[0029]

[0030] In equation (6), X 1 Let X represent the direct bond, the divalent base represented by equation (7), or the divalent base represented by equation (8) independently. 2 The divalent base represented by equation (9) or equation (10), R 8 Each of the following can be used to independently represent an alkyl group or a hydroxyl group having 1 to 4 carbon atoms, and each of the following can be used to independently represent an integer from 0 to 4.

[0031] [Chemistry 3]

[0032]

[0033] In equations (7) and (8), R 9 Each of the following can independently represent an alkyl group or a hydroxyl group having 1 to 4 carbon atoms, and e can independently represent an integer from 0 to 4. In expression (6) , Indicates the bond node that is bonded to the aromatic ring;

[0034] [Chemistry 4]

[0035]

[0036] In equations (9) and (10), R 11 Each of the alkyl groups having 1 to 4 carbon atoms is represented independently, R12 and R 13 Each can independently represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Represents the bond node with the aromatic ring; f independently represents integers from 1 to 4, g represents 1 or 2; where R 12 With R 13 Indicates different substituents.

[0037] [9] The hardened film according to any one of [1] to [8], wherein the polyimide and / or polybenzoxazole has repeating units comprising an acid component and an amine component,

[0038] With the acid and amine components in all repeating units set to 100 mol%, the total of acid and amine components in the total of 200 mol% is between 0 mol% and 40 mol%.

[0039]

[10] The hardened film according to any one of [1] to [9], wherein the polyimide and / or polybenzoxazole comprises repeating units having fluorine atoms directly bonded to sp2 carbons.

[0040]

[11] The hardened film according to

[10] , wherein the polyimide and / or polybenzoxazole has repeating units comprising acid and amine components,

[0041] With the acid and amine components in all repeating units set to 100 mol%, the total of the acid and amine components in the total of 200 mol% is between 5 mol% and 100 mol%.

[0042]

[12] The hardened film according to any one of [1] to

[11] , wherein the molar ratio of silicon atoms to carbon atoms Si (silicon atoms) / C (carbon atoms) obtained when the cross-section of the hardened film is measured using an electron probe microanalyzer is 0.001 or more and 0.005 or less.

[0043]

[13] The hardened film according to any one of [1] to

[12] , wherein the transmittance of light with a wavelength of 450 nm at a film thickness of 2.0 μm is less than 30%.

[0044]

[14] The hardened film according to any one of [1] to

[13] , wherein the optical density (OD) value under visible light per 1 μm film thickness is 0.5 to 1.5.

[0045]

[15] An organic EL display device having a hardened film according to any one of [1] to

[14] .

[0046]

[16] The organic EL display device according to

[15] also has a color filter containing a black matrix.

[0047]

[17] An electronic component having a hardened film according to any one of [1] to

[14] .

[0048] The effects of the invention

[0049] The hardened film of the present invention has excellent long-term reliability, especially when used in organic EL display devices, it can suppress the decrease in luminous brightness during continuous high-temperature driving. Attached Figure Description

[0050] [ Figure 1 [Image] is a cross-sectional view of an example of an organic EL display device.

[0051] [ Figure 2 [ ] is a cross-sectional view of an example of a display device.

[0052] [ Figure 3 [Image] is a schematic diagram of the manufacturing process of an organic EL display device. Detailed Implementation

[0053] The hardened film of the present invention is a hardened film containing polyimide and / or polybenzoxazole, wherein the molar ratio of fluorine to carbon, F (fluorine atoms) / C (carbon atoms) (hereinafter sometimes referred to as F / C ratio), obtained by measuring the cross-section of the hardened film using an electron probe microanalyzer, is 0 or more and 0.05 or less.

[0054] The hardened film of the present invention is a film of a hardened product obtained by hardening the composition.

[0055] Through repeated research, the inventors have determined that by setting the molar ratio (F / C ratio) of fluorine atoms to carbon atoms in the hardened film within the specified range, the long-term reliability of the hardened film is improved, particularly in the case of organic EL display devices, where it can suppress the decrease in luminous brightness during continuous high-temperature operation. While the mechanism is uncertain, it is believed that if the F / C ratio in the hardened film is within the specified range, the gasification of fluorine components from the hardened film or fluorine contamination at openings during processing can be suppressed. Therefore, particularly in organic EL display devices, it can prevent the leaching of fluorine components into the pixel interior or fluorine contamination on the electrode surface, and suppress the decrease in luminous brightness during continuous high-temperature operation.

[0056] From the viewpoint of improving the long-term reliability of the hardened film, particularly in the case of organic EL display devices, suppressing the decrease in luminous brightness during continuous high-temperature driving, the F / C ratio obtained when measuring the cross-section of the hardened film of the present invention using an electron probe microanalyzer is 0 or more and 0.05 or less, preferably 0 or more and 0.03 or less, more preferably 0 or more and 0.02 or less, and even more preferably 0 or more and 0.01 or less, particularly preferably 0. Furthermore, from the viewpoint of improving the reprocessability of the hardened film during manufacturing, the F / C ratio is 0 or more and 0.05 or less, preferably 0.01 or more and 0.05 or less, more preferably 0.02 or more and 0.05 or less, and even more preferably 0.03 or more and 0.05 or less. As a method for measuring the F / C ratio, for example, in the case of an organic EL display device having a hardened film, the hardened film is exposed by decomposing and grinding the display device, and the ratio is determined by measuring the peak intensities of fluorine and carbon using an electron probe microanalyzer through quantitative analysis of standard samples.

[0057] Furthermore, the molar ratio of silicon atoms to carbon atoms (Si (silicon atoms) / C (carbon atoms) – hereinafter sometimes referred to as the Si / C ratio) – obtained by measuring the cross-section of the hardened film using an electron probe microanalyzer is preferably 0.001 or higher and 0.005 or lower. If the Si / C ratio is 0.001 or higher, the bending resistance of the hardened film can be improved. While the mechanism is uncertain, it is believed that if the Si / C ratio is 0.001 or higher, the adhesion to the polyimide film substrate will be improved, thereby suppressing peeling during bending and thus improving bending resistance. On the other hand, if the Si / C ratio is 0.005 or lower, the long-term reliability of the hardened film can be improved, particularly in the case of organic EL display devices, suppressing the decrease in luminous brightness during continuous high-temperature driving. From the viewpoint of improving the bending resistance of the hardened film, the Si / C ratio is preferably 0.001 or higher, more preferably 0.002 or higher, and even more preferably 0.003 or higher. On the other hand, from the viewpoint of improving the long-term reliability of the hardened film, especially in the case of organic EL display devices, suppressing the decrease in luminous brightness during continuous high-temperature driving, the Si / C ratio is preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less. The Si / C ratio can be measured in the same manner as the F / C ratio measured using an electron probe microanalyzer. In order to obtain a hardened film with a Si / C ratio of 0.001 or more and 0.005 or less when measuring the cross-section of a hardened film containing polyimide and / or polybenzoxazole using an electron probe microanalyzer, methods for adjusting the content of acid components with silicon atoms and amine components with silicon atoms in the polyimide and / or polybenzoxazole (described later), or methods for adjusting the content of silane coupling agent (described later), can be listed, but are not limited to these.

[0058] The hardened film of the present invention preferably has a transmittance of 30% or less for light at a wavelength of 450 nm at a film thickness of 2.0 μm. If the transmittance of light at a wavelength of 450 nm is 30% or less, then when the hardened film of the present invention is used in an organic EL display device having an oxide semiconductor thin-film transistor, malfunctions caused by ultraviolet light entering the thin-film transistor (hereinafter referred to as TFT) can be prevented. To prevent ultraviolet light from entering the TFT, the transmittance of light at a wavelength of 450 nm is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The lower limit of the transmittance of light at a wavelength of 450 nm is not particularly limited, but is 0.01% or more. Furthermore, when the film thickness of the hardened film is other than 2.0 μm, the transmittance is converted to absorbance, corrected to absorbance at a film thickness of 2.0 μm, and then the absorbance is converted back to transmittance, thereby obtaining the transmittance of light at a wavelength of 450 nm at a film thickness of 2.0 μm.

[0059] Furthermore, the OD value (optical density) of the hardened film of the present invention under visible light is preferably 0.5 to 1.5 per 1 μm film thickness. If the OD value is 0.5 or higher, the light-shielding property can be improved by the hardened film. Therefore, when the hardened film of the present invention is used in display devices such as organic EL display devices or liquid crystal display devices, external light reflection can be further reduced, and the contrast in image display can be improved. From the viewpoint of reducing reflection, the OD value under visible light per 1 μm film thickness is preferably 0.5 or higher, more preferably 0.6 or higher, and even more preferably 0.7 or higher, and particularly preferably 0.8 or higher. In addition, if the OD value under visible light per 1 μm film thickness is 1.5 or lower, the exposure sensitivity during the fabrication of the hardened film can be improved. From the viewpoint of high sensitivity, the OD value under visible light per 1 μm film thickness is preferably 1.5 or lower, more preferably 1.0 or lower.

[0060] The thickness of the hardened film of the present invention is not particularly limited, but from the viewpoint of ensuring insulation, it is preferably 1.0 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more. Furthermore, from the viewpoint of reducing degassing from the hardened film, the thickness of the hardened film of the present invention is preferably 5.0 μm or less, more preferably 4.0 μm or less, and even more preferably 3.0 μm or less.

[0061] The curing film of the present invention is preferably patterned. Patterning using the curing film of the present invention makes it suitable for applications of the curing film described later.

[0062] As a specific method for obtaining a hardened film, the following can be listed, wherein the hardened film is a hardened film with an F / C ratio of 0 or more and 0.05 or less obtained by patterning and measuring the cross-section of a hardened film containing polyimide and / or polybenzoxazole using an electron probe microanalyzer.

[0063] [Method 1]

[0064] A method for forming a resin film (hereinafter, sometimes referred to as resin film 1) containing a resin composition of a polymer selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, with an F / C ratio of 0 or more and 0.05 or less; forming a photosensitive resin film (hereinafter, sometimes referred to as photosensitive resin film 1) of photoresist on the resin film 1; and then performing exposure, development, etching, removal, and heat treatment of the photosensitive resin film 1.

[0065] [Method 2]

[0066] A method for forming a photosensitive resin film comprising the photosensitive resin composition, wherein the F / C ratio in the solid component after solvent removal from the photosensitive resin composition is 0 or more and 0.05 or less, and the photosensitive resin film is subjected to exposure, development, and heat treatment thereon, wherein the photosensitive resin composition comprises one or more polymers selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, and a photosensitive compound.

[0067] Here, the term "polyimide precursor" refers to a resin that is converted into polyimide through heat treatment or chemical treatment, such as polyamic acid or polyamic acid ester. The term "polybenzoxazole precursor" refers to a resin that is converted into polybenzoxazole through heat treatment or chemical treatment, such as polyhydroxyamide.

[0068] Furthermore, there are no particular limitations on the method for setting the F / C ratio of the hardened film to be 0 or more and 0.05 or less, but method 1 or method 2 is preferred, and method 2 is preferred in terms of simplifying the manufacturing process.

[0069] <Polyimide and / or polybenzoxazole>

[0070] The curing film of the present invention comprises polyimide and / or polybenzoxazole (hereinafter, sometimes referred to as component (a)). By including component (a) in the curing film of the present invention, the long-term reliability of the curing film can be improved, especially in the case of organic EL display devices, it can suppress the decrease in luminous brightness during continuous high-temperature driving.

[0071] (a) Component has repeating units comprising acid and amine components. Furthermore, the acid and amine components referred to herein are respectively repeating units derived from acid and amine components that are the synthetic raw materials of component (a). As repeating units comprising acid and amine components, polyimide has repeating units represented by formula (1), and polybenzoxazole has repeating units represented by formula (2). The curing film of the present invention may contain two or more resins having repeating units represented by formula (1) and resins having repeating units represented by formula (2), or may contain a resin copolymerized from repeating units represented by formula (1) and repeating units represented by formula (2).

[0072] [Chemistry 5]

[0073]

[0074] In formula (1), E represents an organogroup with 4 to 40 carbon atoms and a tetravalent to decavalent valence, and G represents an organogroup with 6 to 40 carbon atoms and a divalent to octavalent valence. R 1 and R 2 Each group independently represents a carboxyl group, a sulfonic acid group, or a hydroxyl group. x and y independently represent integers from 0 to 6. Where x + y > 0.

[0075] [Chemistry 6]

[0076]

[0077] In formula (2), X represents an organogroup with 4 to 40 carbon atoms and a divalent to octavalent charge, and Y represents an organogroup with 6 to 40 carbon atoms and a tetravalent to decavalent charge. 3 and R 4 Each group can independently represent a carboxyl group, a hydroxyl group, or a sulfonic acid group. s and t can independently represent integers from 0 to 6.

[0078] From the viewpoint of reducing the F / C ratio to below 0.05 and improving the long-term reliability of the hardened film, when the content of acid and amine components in all repeating units of component (a) is set to 100 mol%, the total content of acid components with fluorine atoms and amine components with fluorine atoms in the total content of acid and amine components of 200 mol% is preferably 0 mol% or more and 50 mol% or less, more preferably 0 mol% or more and 40 mol% or less, further preferably 0 mol% or more and 20 mol% or less, particularly preferably 0 mol% or more and 10 mol% or less, and most preferably 0 mol%.

[0079] From the viewpoint of improving the bending resistance and long-term reliability of the hardened film by setting the Si / C ratio to 0.001 or more and 0.005 or less, when the content of acid component and amine component in all repeating units of component (a) is set to 100 mol%, the total content of acid component with silicon atoms and amine component with silicon atoms in the total content of acid component and amine component of 200 mol% is preferably 2.5 mol% or more and 12.5 mol% or less, more preferably 3 mol% or more and 11 mol% or less, more preferably 4 mol% or more and 10 mol% or less, and particularly preferably 5 mol% or more and 8 mol% or less.

[0080] From the perspective of improving the reprocessability during the fabrication of the hardened film while maintaining its long-term reliability, component (a) is preferably composed of repeating units containing fluorine atoms directly bonded to sp2 carbons. Reprocessability is improved due to the increased solvent solubility resulting from the inclusion of repeating units containing fluorine atoms in component (a). Furthermore, although the mechanism is uncertain, it is believed that this is because, even with the same F / C ratio in the hardened film, the presence of fluorine atoms directly bonded to sp2 carbons suppresses the vaporization of fluorine components from the hardened film and fluorine contamination at openings during processing, compared to the presence of fluorine atoms directly bonded to sp3 carbons, such as those in CF3 groups.

[0081] Preferably, when the content of acid and amine components in all repeating units of component (a) is set to 100 mol%, the total content of acid components having fluorine atoms directly bonded to the sp2 carbon and amine components having fluorine atoms directly bonded to the sp2 carbon in the total content of 200 mol% of acid and amine components is 5 mol% or more and 100 mol% or less. From the viewpoint of improving the reprocessability during the fabrication of the cured film, the total content of acid components having fluorine atoms directly bonded to the sp2 carbon and amine components having fluorine atoms directly bonded to the sp2 carbon is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. From the viewpoint of improving the long-term reliability of the cured film, the total content of acid components having fluorine atoms directly bonded to the sp2 carbon and amine components having fluorine atoms directly bonded to the sp2 carbon is preferably 100 mol% or less, more preferably 80 mol% or less, and even more preferably 60 mol% or less.

[0082] From the viewpoint of improving the bending resistance of the hardened film, when the content of acid and amine components in all repeating units of component (a) is set to 100 mol%, the total content of acid components with fluorene structures and amine components with fluorene structures in the total content of 200 mol% of acid and amine components is preferably 0 mol% or more and 50 mol% or less. From the viewpoint of improving the bending resistance of the hardened film, the total content of acid components with fluorene structures and amine components with fluorene structures is preferably 50 mol% or less, more preferably 30 mol% or less, more preferably 10 mol% or less, and particularly preferably 0 mol%. On the other hand, from the viewpoint of improving the reprocessability during the fabrication of the hardened film, the content of repeating units with fluorene structures is preferably 10 mol% or more.

[0083] From the viewpoint of improving the solvent solubility of component (a) and improving the reprocessability during the fabrication of the hardened film, component (a) is preferably having residues represented by formula (6).

[0084] [Chemistry 7]

[0085]

[0086] In equation (6), X 1 Let X represent the direct bond, the divalent base represented by equation (7), or the divalent base represented by equation (8) independently. 2 The divalent base represented by equation (9) or equation (10), R 8 Each ...

[0087] [Chemistry 8]

[0088]

[0089] In equations (7) and (8), R 9 Each of the following can be used to independently represent an alkyl group or a hydroxyl group having 1 to 4 carbon atoms, and e can be used to independently represent an integer from 0 to 4. In expression (6) , This indicates the bond node that is bonded to the aromatic ring.

[0090] [Chemistry 9]

[0091]

[0092] In equations (9) and (10), R 11 Each of the alkyl groups having 1 to 4 carbon atoms is represented independently, R 12 and R 13 Each can independently represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. This represents the bond node with the aromatic ring. f represents an integer from 1 to 4 independently, and g represents 1 or 2. Where R... 12 With R 13 Indicates different substituents.

[0093] (a) The residues represented by formula (6) of the component may be contained in either the acid component or the amine component, but are preferably contained in the amine component for the sake of readily available raw materials.

[0094] When the content of acid and amine components in all repeating units of component (a) is set to 100 mol%, the content of residues represented by formula (6) is preferably 5 mol% or more and 100 mol% or less. From the viewpoint of improving the reprocessability during the fabrication of the hardened film, the content of residues represented by formula (6) is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more. From the viewpoint of improving the bending resistance of the hardened film, the content of residues represented by formula (6) is preferably 90 mol% or less, more preferably 80 mol% or less, and more preferably 60 mol% or less.

[0095] From the viewpoint of improving the bending resistance of the hardened film, when the content of acid and amine components in all repeating units of component (a) is set to 100 mol%, the total content of acid and amine components with alicyclic structures in the total content of 200 mol% is preferably 0 mol% or more and 40 mol% or less. From the viewpoint of improving the bending resistance of the hardened film, the total content of acid and amine components with alicyclic structures is preferably 40 mol% or less, more preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less. On the other hand, from the viewpoint of improving the reprocessability during the fabrication of the hardened film, the total content of acid and amine components with alicyclic structures is preferably 10 mol% or more, more preferably 20 mol% or more.

[0096] As a method for determining whether a hardened film contains polyimide and / or polybenzoxazole, for example, an infrared spectrophotometric method for analyzing the hardened film can be cited. Furthermore, regarding the hardened film containing polyimide and / or polybenzoxazole, the total content of acid components with fluorine atoms directly bonded to sp2 carbons and amine components with fluorine atoms directly bonded to sp2 carbons relative to the total content of acid and amine components in all repeating units, the total content of acid components with fluorene structures and amine components with fluorene structures relative to the total content of acid and amine components in all repeating units, the content of residues represented by formula (6) relative to the amine components in all repeating units, and the total content of acid components with alicyclic structures and amine components with alicyclic structures relative to the total content of acid and amine components in all repeating units, can be determined, for example, by thermal decomposition GC / MS: the hardened film is thermally decomposed at 600°C, followed by determination by gas chromatography.

[0097] (a) The component is preferably composed of 5 to 100,000 repeating units represented by formula (1) or formula (2). In addition to having repeating units represented by formula (1) or formula (2), other repeating units may also be included. In the case described above, the component (a) is preferably composed of repeating units represented by formula (1) or formula (2) that account for more than 50 mol% of all repeating units in 100 mol%.

[0098] In the above equation (2), X(R) 3 ) s Residues representing acids. X is an organogroup with 4 to 40 carbon atoms and a divalent to octavalent oxidation state, preferably a divalent to octavalent organogroup containing an aromatic ring or a cyclic aliphatic group. Examples of acid residues are shown below, but component (a) may have two or more acid residues shown below as X(R) in formula (2). 3 ) s .

[0099] Examples of acid residues containing fluorine atoms include: residues of dicarboxylic acids such as 2,2-bis(4-carboxyphenyl)hexafluoropropane, tetrafluoroterephthalic acid, and tetrafluoroisophthalic acid; residues of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,4-difluoro-2,3,4,5-benzenetetracarboxylic acid, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzoic acid, hexafluorooxydiphthalic acid, and residues of aromatic tetracarboxylic acids with the structures shown below.

[0100] [Chemistry 10]

[0101]

[0102] R 21 and R22 Each can be used to represent a hydrogen atom or a hydroxyl group independently.

[0103] Examples of acid residues that do not contain fluorine atoms include: residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; residues of tricarboxylic acids such as trimellitic acid, pyromellitic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; pyromellitic tetracarboxylic acid; 3,3',4,4'-biphenyltetracarboxylic acid; 2,3,3',4'-biphenyltetracarboxylic acid; 2,2',3,3'-biphenyltetracarboxylic acid; 3,3',4,4'-benzophenone tetracarboxylic acid; 2,2',3,3'-benzophenone tetracarboxylic acid; and 1,1-bis(3-)-(2 ... Residues of tetracarboxylic acids, including (4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, aromatic tetracarboxylic acids with the structures shown below, or aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic acid.

[0104] [Chemistry 11]

[0105]

[0106] R 20 Represents an oxygen atom, SO2, or C(CH3)2. R 21 and R 22 Each can be used to represent a hydrogen atom or a hydroxyl group independently.

[0107] In the above equation (1), E(R) 1 ) x Residues of acid dianhydrides. E is an organogroup with 4 to 40 carbon atoms and a tetravalent to decavalent oxidation state, preferably an organogroup containing an aromatic ring or a cyclic aliphatic group. Examples of acid dianhydride residues are shown below, but component (a) may have two or more acid dianhydride residues shown below as E(R) in formula (1). 1 ) x .

[0108] Examples of dianhydrides containing fluorine atoms include residues of aromatic tetracarboxylic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,4-difluoro-2,3,4,5-benzenetetracarboxylic acid dianhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzoic acid dianhydride, hexafluorooxydiphthalic acid dianhydride, and other dianhydrides with structures shown below.

[0109] [Chemistry 12]

[0110]

[0111] R 21 and R 22 Each can be used to represent a hydrogen atom or a hydroxyl group independently.

[0112] Examples of dianhydrides that do not contain fluorine atoms include: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, Residues of aromatic tetracarboxylic anhydrides such as bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic anhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, and acid dianhydrides with the structures shown below, or aliphatic tetracarboxylic anhydrides such as butanetetracarboxylic anhydride, and aliphatic tetracarboxylic anhydrides containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic anhydride.

[0113] [Chemistry 13]

[0114]

[0115] R 20 Represents an oxygen atom, SO2, or C(CH3)2. R 21 and R 22 Each can be used to represent a hydrogen atom or a hydroxyl group independently.

[0116] In equation (2), Y(R) 4 ) t and G(R) in equation (1) 2 ) yResidues representing diamines or dihydroxydiamines. Y is an organogroup having 6 to 40 carbon atoms and a tetravalent to decavalent charge, preferably a tetravalent to decavalent organogroup containing an aromatic ring or a cyclic aliphatic group. G is an organogroup having 6 to 40 carbon atoms and a divalent to octavalent charge, preferably a divalent to octavalent organogroup containing an aromatic ring or a cyclic aliphatic group. Examples of residues representing diamines and dihydroxydiamines are shown below, but component (a) may have two or more of the residues shown below as Y(R) in formula (2). 4 ) t and G(R) in equation (1) 2 ) y .

[0117] As residues of diamines and dihydroxydiamines containing fluorine atoms, they may contain: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybiphenylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,4'-diaminooctafluorobiphenyl, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 2-fluoro-1,4-phenylenediamine, Residues of aromatic diamines, such as 2,5-difluoro-1,4-phenylenediamine, 4,4'-diamino-2,2'-difluorobiphenyl, 4,4'-diamino-3,3'-difluorobiphenyl, 4,4'-diamino-2,5,2', 5'-tetrafluorobiphenyl, 4,4'-diamino-2,6,2', 6'-tetrafluorobiphenyl, 4,4'-diaminooctafluorodiphenyl ether, compounds formed by substituting at least a portion of the hydrogen atoms of these aromatic rings with alkyl or halogen atoms, and residues of diamines with the structures shown below.

[0118] [Chemistry 14]

[0119]

[0120] R 21 ~R 22 Each can be used to represent a hydrogen atom or a hydroxyl group independently.

[0121] As residues of diamines and dihydroxydiamines that do not contain fluorine atoms, they may contain: 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(3-amino-4-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxy) Residues of aromatic diamines and dihydroxydiamines, such as phenylpropane, 4,6-diaminoresorcinol, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 3,3'-diamino-[1,1'-biphenyl]-4,4'-diol, compounds formed by substituting at least a portion of the hydrogen atoms of these aromatic rings using alkyl or halogen atoms, residues of aliphatic diamines containing cyclic aliphatic groups such as cyclohexyldiamine and methylenebicyclohexylamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, α,ω-diaminopolydimethylsiloxane, α,ω - Residues of silicon-containing diamines such as bis(3-aminopropyl)polydimethylsiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, bis(10-aminodemethylene)tetramethyldisiloxane, bis(3-aminophenoxymethyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polymethylphenylsiloxane, α,ω-bis(3-aminopropyl)poly(dimethylsiloxane-diphenylsiloxane) copolymer, residues of diamines with the structures shown below, and residues of diamines having residues represented by the formula (6) described above.

[0122] [Chemistry 15]

[0123]

[0124] R 20 Represents an oxygen atom, SO2, or C(CH3)2. R 21 ~R 24 Each can be used to represent a hydrogen atom or a hydroxyl group independently.

[0125] From the perspective of improving the solvent solubility of component (a) and enhancing the reprocessability during the fabrication of the hardened film, X in equation (6)1 Direct bonds are preferred. On the other hand, from the viewpoint of improving sensitivity during the fabrication of the hardened film, X... 1 Preferably, it is a divalent base represented by formula (7) or formula (8), and more preferably, it is a divalent base represented by formula (7). X in formula (6) 2 From the viewpoint of improving the bending resistance of the hardened film, the divalent group represented by formula (9) or formula (10) is preferably the one represented by formula (10). 8 Each of the alkyl or hydroxyl groups having 1 to 4 carbon atoms is independently represented. From the viewpoint of improving the solvent solubility of component (a), alkyl groups having 1 to 4 carbon atoms are preferred, and methyl groups are preferred. Each of the d groups is independently represented as an integer from 0 to 4. From the viewpoint of improving the solvent solubility of component (a), d is preferably an integer from 1 to 4.

[0126] In equations (7) and (8), R 9 From the viewpoint that the alkyl or hydroxyl groups having 1 to 4 carbon atoms can be independently represented, methyl is preferred, which can improve the heat resistance of component (a). From the viewpoint that the integers e can be independently represented, d is preferred, which can be an integer of 1 to 4, which can improve the solvent solubility of component (a). In expression (6) , This indicates the bond node that is bonded to the aromatic ring.

[0127] In equation (9), R 11 In terms of improving the heat resistance of component (a), methyl groups are preferred, as each alkyl group having 1 to 4 carbon atoms can be independently represented. g represents 1 or 2, and f represents an integer from 1 to 4, thus balancing the heat resistance and solvent solubility of component (a) is desirable. In formula (10), R... 12 and R 13 Each of the following groups independently represents a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Regarding its ability to improve the heat resistance of component (a), R... 12 R 13 Preferably, each group is an independently saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably an saturated hydrocarbon group having 1 to 6 carbon atoms. Wherein, R 12 With R 13 This indicates different substituents. The "different substituents" referred to here, excluding R, include... 12 With R 13 The relationship includes not only those with different compositional formulas, but also structural isomers with the same compositional formula but different bonding states between atoms. This is achieved through R... 12 With R 13 Different substituents can improve the solvent solubility of component (a). From the viewpoint of improving the solvent solubility of component (a), R... 12 With R 13The difference in the number of carbons is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. As the substituents represented by formulas (9) and (10), examples of substituents shown below can be listed.

[0128] [Chemistry 16]

[0129]

[0130] Alternatively, existing monoamines, anhydrides, acyl chlorides, monocarboxylic acids, and reactive ester compounds with acidic groups can be used to seal the ends of these resins.

[0131] Component (a) can be synthesized using existing methods, but preferably using a solvent containing β-alkoxypropionamide as the polymerization solvent. By using a polymerization solvent containing β-alkoxypropionamide for component (a), component (a) containing β-alkoxypropionamide can be obtained. When the resin composition is heat-treated, a hardened film containing β-alkoxypropionamide can be obtained. The presence of β-alkoxypropionamide in the hardened film improves its long-term reliability.

[0132] The hardened film of the present invention may contain a resin other than component (a). Examples of resins other than component (a) include polymers of free radical polymerizable monomers having acidic groups, caloric resins, phenolic resins, siloxane resins, etc., but are not limited thereto.

[0133] Examples of polymers that are free radical polymerizable monomers with acidic groups include acrylic resins, polyhydroxystyrene, and / or copolymers of polyhydroxystyrene / polystyrene. Existing materials can be used as free radical polymerizable monomers with acidic groups, such as: o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, and their alkyl-substituted or alkoxy-substituted derivatives; methacrylic acid and acrylic acid, and their α-haloalkyl-substituted, alkoxy-substituted, halogen-substituted, nitro-substituted, or cyano-substituted derivatives.

[0134] From the viewpoint of improving the long-term reliability of the curing film, particularly in the case of organic EL display devices where it suppresses the decrease in luminous brightness during continuous high-temperature driving, the curing film of the present invention preferably contains polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer. In the present invention, the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer 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, relative to 100 parts by mass of component (a). By setting the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer to 5 parts by mass or more relative to 100 parts by mass of component (a), the long-term reliability of the curing film can be improved. In addition, the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less, relative to 100 parts by mass of component (a). By setting the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer to 60 parts by mass or less relative to 100 parts by mass of component (a), the chemical resistance of the curing film can be maintained.

[0135] Methods for confirming whether a hardened film contains polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymers include, for example: analyzing the hardened film using infrared spectroscopy; analyzing the hardened film by thermal decomposition GC / MS, i.e., analyzing the hardened film by gas chromatography after thermal decomposition at 600°C; extracting components from the hardened film using organic solvents and measuring the extract using liquid chromatography; and measuring the components in the hardened film using time-of-flight secondary ion mass spectrometry, etc.

[0136] Examples of calorie resins include those with a calorie structure, i.e., resins with a framework structure in which two ring structures are bonded to the quaternary carbon atoms that form the ring structure. A calorie structure is generally a structure in which a benzene ring is bonded to a fluorene ring.

[0137] Examples of phenolic resins include existing phenolic varnish phenolic resins or methyl phenolic resins obtained by polycondensing various phenols individually or in mixtures thereof using aldehydes such as formaldehyde.

[0138] Examples of siloxane resins include conventional siloxane resins obtained by hydrolyzing one or more of tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes to induce dehydration and condensation.

[0139] <Aromatic hydrocarbon compounds having at least three phenolic hydroxyl groups within an aromatic ring>

[0140] The curing film of the present invention is preferably an aromatic hydrocarbon compound containing at least three phenolic hydroxyl groups within an aromatic ring (hereinafter, sometimes referred to as component (b)). By including component (b) in the curing film of the present invention, the long-term reliability of the curing film can be improved, and in particular, in the case of organic EL display devices, the decrease in luminous brightness during continuous high-temperature driving can be suppressed.

[0141] Methods for confirming whether a hardened film contains component (b) include, for example, the following: thermal decomposition GC / MS, i.e., analysis by gas chromatography after thermal decomposition of the hardened film at 600°C; extraction of components from the hardened film using organic solvents and determination of the extract by liquid chromatography; determination of components in the hardened film using time-of-flight secondary ion mass analysis, etc.

[0142] The aromatic hydrocarbon structure possessed by component (b) can be exemplified by existing monocyclic or condensed polycyclic structures. Furthermore, the aromatic hydrocarbon has at least three phenolic hydroxyl groups within one aromatic ring. In this invention, the state of having at least three phenolic hydroxyl groups within one aromatic ring refers to the state of having at least three phenolic hydroxyl groups within a single aromatic ring; for example, compounds containing three aromatic rings each having one phenolic hydroxyl group are not included in component (b) of this invention. Specifically, as component (b), compounds having the structures shown below can be listed, but are not limited thereto.

[0143] [Chemistry 17]

[0144]

[0145] R 7 Independently represent a monovalent organogroup with 1 to 20 carbon atoms, where k represents an integer from 0 to 2, l represents an integer from 0 to 7, and m represents an integer from 3 to 10. Wherein, {(2k+6)-(l+m)}≥0.

[0146] Examples of aromatic hydrocarbons having at least three phenolic hydroxyl groups within an aromatic ring include: phloroglucinol, gallophenol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-isopropylidene di-gallotol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizarin.

[0147] From the viewpoint that, when combined with the thermal crosslinking agent described later, the transmittance of light from 300 nm to 500 nm of the hardened film is further reduced, i.e., the transmittance of light with a wavelength of 450 nm is set to 30% or less, as component (b), the substitution position of at least one of the phenolic hydroxyl groups other than any of the phenolic hydroxyl groups in component (b) is preferably ortho or para, more preferably para.

[0148] Compounds (b1) in which at least one of the phenolic hydroxyl groups other than any of the phenolic hydroxyl groups in component (b) is substituted at an ortho position, for example: gallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-isopropylidene di-gallotol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, etc. From the viewpoint of further reducing the light transmittance of the hardened film from 300 nm to 500 nm when combined with the thermal crosslinking agent described later, gallophenol or 1,2,4-trihydroxybenzene is preferred. Examples of compounds (b2) in component (b) where at least one of the phenolic hydroxyl groups other than any of the phenolic hydroxyl groups 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, quinone leucocyanide, etc. From the viewpoint of further reducing the light transmittance of the hardened film from 300 nm to 500 nm when combined with the thermal crosslinking agent described later, 1,2,4-trihydroxybenzene is preferred.

[0149] (b) There is no particular upper limit to the molecular weight of the component, but it is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. (b) The lower limit to the molecular weight of the component is 126 or more.

[0150] In this invention, the content of component (b) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of component (a). By setting the content of component (b) to 1 part by mass or more relative to 100 parts by mass of component (a), the long-term reliability of the hardened film of this invention can be improved. Furthermore, the content of component (b) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, relative to 100 parts by mass of component (a). By setting the content of component (b) to 50 parts by mass or less relative to 100 parts by mass of component (a), the chemical resistance of the hardened film can be maintained.

[0151] <Compounds derived from photosensitive compounds>

[0152] The curing film of the present invention preferably contains a compound derived from a photosensitive compound (hereinafter, sometimes referred to as component (c)). By including a compound derived from a photosensitive compound in the curing film of the present invention, the manufacturing process of the curing film can be simplified. Examples of component (c) include photopolymerization initiators (hereinafter, sometimes referred to as component (c1)) and naphthoquinone diazide compounds (hereinafter, sometimes referred to as component (c2)).

[0153] As component (c1), existing photopolymerization initiators can be listed. Examples include: benzoyl ketal compounds, α-hydroxy ketal compounds, α-amino ketal compounds, acylphosphine oxide compounds, biimidazole compounds, oxime ester compounds, acridine compounds, dicene compounds, benzophenone compounds, acetophenone compounds, aromatic ketone ester compounds, or benzoic acid ester compounds. From the viewpoint of improving sensitivity during the fabrication of the curing film, the curing film of the present invention is preferably an α-hydroxy ketal compound, an α-amino ketone compound, an acylphosphine oxide compound, a biimidazole compound, or an oxime ester compound; from the viewpoint of improving sensitivity during exposure, improving halftone characteristics, and suppressing residue after development, an oxime ester compound is further preferred.

[0154] Methods for confirming whether the hardened film contains compounds derived from component (c) include, for example, the following: analysis by thermal decomposition GC / MS, i.e., analysis by gas chromatography after thermal decomposition of the hardened film at 600°C; extraction of components in the hardened film using organic solvents and determination of the extract by liquid chromatography; determination of components in the hardened film using time-of-flight secondary ion mass analysis, etc.

[0155] From the viewpoint of improving the sensitivity during the fabrication of the hardened film of the present invention, the content of the compound derived from component (c1) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of component (a). On the other hand, from the viewpoint of suppressing residues during the fabrication of the hardened film of the present invention, the content of the compound derived from component (c1) is preferably 50 parts by mass or less, relative to 100 parts by mass of component (a).

[0156] As component (c2), existing naphthoquinone diazide compounds can be listed. For example, 1,2-naphthoquinone diazide-5-sulfonate compounds and / or 1,2-naphthoquinone diazide-4-sulfonate compounds can be listed.

[0157] From the viewpoint of improving the long-term reliability of the hardened film of the present invention, the compound derived from the photosensitive compound included in the hardened film of the present invention is preferably a compound derived from component (c2). Specifically, compounds derived from naphthoquinone diazide compounds can be selected from one or more compounds selected from the group consisting of carboxylic acids containing an indene structure, carboxylic acid esters containing an indene structure, sulfonic acids containing an indene structure, and aryl sulfonates containing an indene structure. Preferably, it is a compound selected from one or more compounds selected from the group consisting of carboxylic acids containing an indene structure, carboxylic acid esters containing an indene structure, sulfonic acids containing an indene structure, and aryl sulfonates containing an indene structure.

[0158] From the viewpoint of improving the sensitivity during the fabrication of the hardened film of the present invention, the content of the compound derived from component (c2) is preferably 0.1 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 25 parts by mass or more, relative to 100 parts by mass of component (a). On the other hand, from the viewpoint of suppressing residues during the fabrication of the hardened film of the present invention, the content of the compound derived from component (c2) is preferably 100 parts by mass or less, relative to 100 parts by mass of component (a).

[0159] <β-alkoxypropionamide>

[0160] The curing film of the present invention preferably contains β-alkoxypropionamide. By including β-alkoxypropionamide in the curing film of the present invention, the long-term reliability of the curing film can be improved, particularly in the case of organic EL display devices, it can suppress the decrease in luminous brightness during continuous high-temperature driving.

[0161] Specific methods for obtaining a hardened film containing β-alkoxypropionamide include: a method of adding β-alkoxypropionamide to a resin composition for obtaining the hardened film of the present invention and then heat-treating the resin composition to obtain a hardened film; and a method of heat-treating a resin composition containing component (a) of β-alkoxypropionamide by using β-alkoxypropionamide as a polymerization solvent for component (a). From the viewpoint of suppressing the volatilization of β-alkoxypropionamide during heat treatment and improving the long-term reliability of the hardened film, the method of heat-treating a resin composition containing component (a) of β-alkoxypropionamide by using β-alkoxypropionamide as a polymerization solvent for component (a) to obtain a hardened film is preferred.

[0162] As a method to confirm whether the hardened film contains β-alkoxypropionamide, for example, a method can be listed as follows: for components generated from the hardened film, adsorption and trapping are performed using a purge and trapping method, followed by thermal decomposition at 600°C, and then analysis is performed using purge and trapping GC / MS determined by gas chromatography.

[0163] Examples of β-alkoxypropionamides include: β-methoxypropionamide, β-methoxy-N-methylpropionamide, β-methoxy-N,N-dimethylpropionamide, β-methoxy-N-ethylpropionamide, β-methoxy-N,N-diethylpropionamide, β-methoxy-(N-propyl)propionamide, β-methoxy-(N,N-dipropyl)propionamide, β-methoxy-N-butylpropionamide, β-methoxy-N,N-dibutylpropionamide, β-ethoxy-N,N-dimethylpropionamide, β-propoxy-N,N-dimethylpropionamide, and β-butoxy-N,N-dimethylpropionamide. From a general point of view, β-methoxy-N,N-dimethylpropionamide or β-butoxy-N,N-dimethylpropionamide is preferred as a β-alkoxypropionamide.

[0164] From the viewpoint of improving the long-term reliability of the hardened film, the content of β-alkoxypropionamide in the hardened film is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less, and even more preferably 0.1% by mass or more and 0.5% by mass or less.

[0165] <Sulfonic acid and / or sulfonate ions>

[0166] The hardened film of the present invention preferably contains one or more sulfonic acids selected from the group represented by any one of formulas (3) to (5), or sulfonate ions derived from said sulfonic acid (hereinafter, sometimes referred to as specific sulfonic acids and / or sulfonate ions).

[0167] [Chemistry 18]

[0168]

[0169] In equation (3), R 5 Each of these can independently represent a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, where n represents an integer from 1 to 5. In equation (4), R 6 A monovalent organic group representing 1 to 10 carbon atoms.

[0170] The curing film of the present invention contains specific sulfonic acid and / or sulfonate ions, which can improve the long-term reliability of the curing film, especially in the case of organic EL display devices, it can suppress the decrease in luminous brightness during continuous high-temperature driving.

[0171] Specific methods for obtaining a hardened film containing specific sulfonic acids and / or sulfonate ions include methods for obtaining a hardened film by heat-treating a composition using a compound containing specific sulfonic acids and / or sulfonate ions; methods for obtaining a hardened film by heat-treating a composition containing a hot acid generating agent that generates specific sulfonic acids and / or sulfonate ions during heat treatment; and, from the viewpoint of improving the long-term reliability of the hardened film, methods for obtaining a hardened film by heat-treating a composition containing a hot acid generating agent that generates specific sulfonic acids and / or sulfonate ions during heat treatment.

[0172] Methods for confirming whether a hardened membrane contains specific sulfonic acids and / or sulfonate ions include, for example, the following: thermal decomposition GC / MS analysis, i.e., analysis by gas chromatography after thermal decomposition of the hardened membrane at 600°C; extraction of components from the hardened membrane using organic solvents and determination of the extract by liquid chromatography; and determination of components in the hardened membrane using time-of-flight secondary ion mass analysis.

[0173] As a hot acid generating agent that produces specific sulfonic acid and / or sulfonate ions during heat treatment, a hot acid generating agent having a sulfonate ester structure is preferred. Specifically, examples include: Irgacure (registered trademark) PAG103, PAG121 (trade name, manufactured by BASF Japan), PA-411, PA-480 (trade name, manufactured by Heraeus), PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, and PAI-1004 (trade name, manufactured by Midori Chemicals). (manufactured by Kagaku (stock)), SP-082, SP-601, SP-606, SP-607, SP-612 (trade name, manufactured by ADEKA (stock)), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (trade name, manufactured by Heraeus (stock)), NAI-105, NAI-106, NAI-109 (trade name, manufactured by Midori Kagaku (stock)), and sulfonates synthesized using one or more sulfonic acids selected from the group represented by formulas (3) to (5) with alcohols or phenols and using existing methods.

[0174] In equation (3), R 5 Each of the following can be independently represented: a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, where n is an integer from 1 to 5. Examples of monovalent organic groups having 1 to 10 carbon atoms include: alkyl, alkynyl, alkenyl, aryl, CF3, etc. From the viewpoint of readily available raw materials, R5 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group. From the viewpoint of readily available raw materials, n is preferably an integer from 1 to 3, and more preferably 1. Examples of sulfonic acids represented by formula (3) include: benzenesulfonic acid, toluenesulfonic acid, styrenesulfonic acid, etc.

[0175] In equation (4), R 6 This refers to a monovalent organometallic group having 1 to 10 carbon atoms. Examples of monovalent organometallic groups having 1 to 10 carbon atoms include: alkyl, alkynyl, alkenyl, benzyl, CF3, etc. From the perspective of readily available raw materials, R... 5 Preferably, it is an alkyl group having 1 to 10 carbon atoms or CF3, and more preferably an alkyl group having 1 to 10 carbon atoms. Examples of sulfonic acids represented by formula (4) include: methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octylsulfonic acid, trifluoromethanesulfonic acid, benzylsulfonic acid, vinylsulfonic acid, etc.

[0176] From the viewpoint of improving the long-term reliability of the hardened film, the content of the specific sulfonic acid and / or sulfonate ions is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, relative to 100 parts by mass of component (a). On the other hand, from the viewpoint of improving the heat resistance of the hardened film, the content of the specific sulfonic acid and / or sulfonate ions is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of component (a).

[0177] <Coloring agent (d)>

[0178] The curing film of the present invention preferably also contains a colorant (d) (hereinafter, sometimes referred to as the (d) component). By including the (d) component in the curing film of the present invention, the light-shielding properties of the curing film can be improved, and external light reflection can be suppressed when used in a display device. Furthermore, by including the (d) component in the curing film of the present invention, the transmittance of light at a wavelength of 450 nm can be reduced. When using the curing film of the present invention in an organic EL display device having an oxide semiconductor TFT, malfunctions caused by ultraviolet light entering the TFT can be prevented. From the viewpoint of improving the visible light shielding properties of the curing film and increasing the OD value under visible light per 1 μm film thickness, the (d) component preferably has a maximum absorption wavelength in any range within the wavelength range of 300 nm or more and 850 nm or less. Furthermore, from the viewpoint of setting the transmittance of light at a wavelength of 450 nm to 30% or less, the (d) component preferably has a maximum absorption wavelength in any range within the wavelength range of 300 nm or more and 600 nm or less, and more preferably in any range within the wavelength range of 400 nm or more and 500 nm or less.

[0179] As component (d), it is preferred to contain a dye (d1) and / or a pigment (d2). Component (d) preferably contains at least one, for example, it may contain one dye (d1) or pigment (d2), or two or more dyes (d1) or pigments (d2), or one or more dyes (d1) and one or more pigments (d2). In addition, as component (d), it is preferred to be a black agent and / or a mixture of two or more colorants.

[0180] From the viewpoint of solvent solubility, component (d) in the hardened film of the present invention preferably contains a dye (d1). Furthermore, from the viewpoint of improving the sensitivity during the manufacture of the hardened film of the present invention, the dye (d1) is preferably an ionic dye that forms ion pairs between organic ions. In addition, from the viewpoint of increasing sensitivity and reducing residue, component (d) preferably has sulfonic acid groups and / or sulfonate groups.

[0181] Examples of possible backbone structures for dyes (d1) include, but are not limited to, anthraquinone, azo, phthalocyanine, methine, oxazine, quinoline, triarylmethane, and xanthones. Among these, anthraquinone, azo, methine, triarylmethane, or xanthones are preferred from the viewpoint of solvent solubility or heat resistance. Furthermore, xanthones are even more preferred from the viewpoint of improving heat resistance. These dyes can be used individually or in the form of metal complex salts.

[0182] From the viewpoint of improving the heat resistance of the hardened film, component (d) of the present invention is preferably a pigment (d2). As pigment (d2), organic black pigment is particularly preferred, and preferably includes one or more pigments selected from the group consisting of benzofuranone black pigments, perylene black pigments, and azo black pigments.

[0183] The content of component (d) is preferably 0.1 to 300 parts by mass relative to 100 parts by mass of component (a), more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass. By setting the content of component (d) to 0.1 parts by mass or more relative to 100 parts by mass of component (a), light of the corresponding wavelength can be absorbed. Furthermore, by setting the content of component (d) to 300 parts by mass or less, light of the corresponding wavelength can be absorbed while maintaining the heat resistance and mechanical properties of the hardened film.

[0184] <Compounds derived from thermal crosslinking agents>

[0185] The hardened film of the present invention may also contain a compound derived from a thermal crosslinking agent. A thermal crosslinking agent is a compound having at least two thermally reactive functional groups such as alkoxymethyl, hydroxymethyl, epoxy, or oxetyl in its molecule. By containing a compound derived from a thermal crosslinking agent in the hardened film of the present invention, the thermal crosslinking agent crosslinks with component (a) or with itself, thereby improving the heat resistance, chemical resistance, and bending resistance of the hardened film. When used in conjunction with component (b), the transmittance of light at 300 nm to 500 nm after hardening is reduced. From this perspective, alkoxymethyl or hydroxymethyl is preferred as the thermal crosslinking agent, and more preferably alkoxymethyl or hydroxymethyl having direct nitrogen atom substitution. When used in conjunction with component (b), the transmittance of light at 300 nm to 500 nm after hardening is reduced. From this perspective, the compound derived from the thermal crosslinking agent preferably has a triazine ring.

[0186] The content of the compound derived from the thermal crosslinking agent is preferably 1% by mass or more and 30% by mass or less in 100% by mass of the hardened film. If the content of the compound derived from the thermal crosslinking agent is 1% by mass or more, the chemical resistance and flexural strength of the hardened film can be further improved. In addition, if the content of the compound derived from the thermal crosslinking agent is 30% by mass or less, the amount of gas escaping from the hardened film can be further reduced.

[0187] <Compounds derived from close-fitting modifiers>

[0188] The hardened film of the present invention may also contain compounds derived from adhesion modifiers. These compounds may include those derived from existing silane coupling agents, titanium chelating agents, aluminum chelating agents, or compounds obtained by reacting aromatic amine compounds with alkoxy-containing silicon compounds. Two or more of these compounds may be included. By containing compounds derived from these adhesion modifiers, the adhesion between the hardened film and substrates such as silicon wafers, indium tin oxide (ITO), SiO2, silicon nitride, and polyimide film substrates can be improved.

[0189] From the viewpoint of improving the bending resistance and long-term reliability of the hardened film by setting the Si / C ratio to 0.001 or higher and 0.005 or lower, the hardened film of the present invention preferably contains a conventional silane coupling agent as a bonding modifier. Examples of conventional silane coupling agents include: vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacrylateoxypropylmethyldimethoxysilane, 3-methacrylateoxypropyltrimethoxysilane, 3-methacrylateoxypropyltriethoxysilane, 3-methacrylateoxypropyltriethoxysilane, 3-methacrylateoxypropyltrimethoxysilane, 3-methacrylateoxypropyltriethoxysilane, 3-methacrylateoxypropyltrimethoxysilane, 3-methacrylateoxypropyltriethoxysilane, 3-methylpropaneoxypropyltrimethoxysilane, 3-methacrylateoxypropyltrieth ... Acrylic oxypropyltriethoxysilane, 3-acrylic oxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureopropyltrialkoxysilane, 3-ureopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. From the viewpoint of improving storage stability, one or more silane coupling agents selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane are preferred, and 3-glycidoxypropyltrimethoxysilane is more preferred.

[0190] The content of the adhesion modifier is preferably 0.01% to 10% by mass in 100% by mass of the hardened film. From the viewpoint of improving the bending resistance and long-term reliability of the hardened film by setting the Si / C ratio to 0.001 or more and 0.005 or less, when the hardened film of the present invention contains a conventional silane coupling agent as an adhesion modifier, the content of the conventional silane coupling agent is preferably 0.6% to 6.0% by mass in 100% by mass of the hardened film, more preferably 1.0% to 5.0% by mass, and particularly preferably 2.0% to 4.0% by mass.

[0191] <Inorganic Particles>

[0192] The hardened film of the present invention may also contain inorganic particles. Preferred examples of inorganic particles include those containing silicon oxide, titanium oxide, barium titanate, aluminum oxide, talc, etc. The primary particle size of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0193] The content of inorganic particles in the hardened film is preferably 5% to 90% by mass in 100% by mass.

[0194] <Method for manufacturing hardened film>

[0195] The method for manufacturing the hardened film of the present invention will be described using the following method as an example: a photosensitive resin film comprising a photosensitive resin composition is formed on a substrate, and the photosensitive resin film is exposed and developed and then subjected to heat treatment.

[0196] First, the process of forming a photosensitive resin film containing a photosensitive resin composition on a substrate will be described.

[0197] The photosensitive resin composition used in the manufacture of the hardened film of the present invention can be obtained, for example, by mixing and dissolving one or more polymers selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof with component (c), component (b) as needed, β-alkoxypropionamide, a hot acid generating agent that generates specific sulfonic acid and / or sulfonate ions, component (d), a thermal crosslinking agent, a bonding modifier, a surfactant, inorganic particles, a solvent, etc.

[0198] Subsequently, the photosensitive resin composition is coated onto a substrate to obtain a coated film of the photosensitive resin composition, and the coated film is dried to obtain a photosensitive resin film. As the substrate, an existing substrate such as a glass substrate can be used. Examples of methods for coating the photosensitive resin composition of the present invention include spin coating, slot coating, dip coating, spray coating, and printing.

[0199] After coating the photosensitive resin composition, a vacuum drying process is performed as needed. The vacuum drying rate also depends on the vacuum chamber volume, vacuum pump capacity, or the diameter of the piping between the chamber and the pump. For example, it is preferable to set the condition to reduce the pressure to 40 Pa after 60 seconds in the vacuum chamber without a coated substrate.

[0200] Generally, after coating or vacuum drying, the obtained coated film is heated and dried. This process is also called pre-baking. Drying is performed using heating plates, ovens, infrared radiation, etc. When using heating plates, heating is performed directly on the plate, or the coated film is held in place on a clamp such as a fixing pin on the plate for heating. The heating time is preferably from 1 minute to several hours. The heating temperature varies depending on the type or purpose of the coated film, but from the viewpoint of promoting solvent drying during pre-baking, it is preferably 80°C or higher, and more preferably 90°C or higher. On the other hand, from the viewpoint of reducing the hardening process during pre-baking, the heating temperature is preferably 150°C or lower, and more preferably 140°C or lower.

[0201] Next, the process of exposing the photosensitive resin film will be described. For example, for a photosensitive resin film, chemical rays are irradiated through a photomask having the desired pattern, thereby exposing and developing the film to form the desired pattern.

[0202] Examples of chemical rays used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In this invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp are preferred. When the photosensitive resin film has positive photosensitivity, the exposed portion dissolves in the developing solution. When the photosensitive resin film has negative photosensitivity, the exposed portion hardens and becomes insoluble in the developing solution.

[0203] Next, the process of developing the exposed photosensitive resin film will be explained.

[0204] After exposure, if the photosensitive resin film is positive, the exposed areas are removed using a developing solution; if the photosensitive resin film is negative, the unexposed areas are removed using a developing solution, thereby forming the desired pattern. The developing solution is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. Polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone can be added to these alkaline aqueous solutions. Examples of development methods include spraying, puddle, immersion, and ultrasonic methods.

[0205] Next, the pattern formed by development is preferably rinsed with distilled water. Alcohols such as ethanol and isopropanol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate can be added to the distilled water for rinsing.

[0206] Next, the process of heating the developed photosensitive resin film to obtain a hardened film will be described.

[0207] A hardened film can be obtained by heat treatment of the developed photosensitive resin film as described. When the photosensitive resin composition used in the manufacture of the hardened film of the present invention contains a polyimide precursor or a polybenzoxazole precursor, a hardened film containing polyimide or polybenzoxazole can be obtained by heat treatment.

[0208] From the viewpoint of further reducing the amount of gas escaping from the hardened film, the heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher. On the other hand, from the viewpoint of improving the toughness of the hardened film, the heat treatment temperature is preferably 500°C or lower, more preferably 450°C or lower. Within the temperature range, the temperature can be increased in stages or continuously. From the viewpoint of further reducing the amount of gas escaping, the heat treatment time is preferably 30 minutes or higher. In addition, from the viewpoint of improving the toughness of the hardened film, the heat treatment time is preferably 3 hours or less. For example, methods such as performing heat treatment at 150°C and 250°C for 30 minutes each, or performing heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours, can be cited.

[0209] From the viewpoint of improving the long-term reliability of the hardened film, especially in the case of organic EL display devices, and suppressing the decrease in luminous brightness during continuous high-temperature operation, the environment for heat treatment is preferably a low oxygen concentration of less than 5%. Examples of inert gases used for setting the oxygen concentration to less than 5% include nitrogen or argon. The oxygen concentration in the inert gas environment is preferably less than 5%, more preferably less than 1%, and even more preferably less than 0.5%, particularly preferably less than 0.01%.

[0210] <Examples of Hardened Film Applications>

[0211] The hardened film of the present invention is preferably used as a surface protective layer or interlayer insulating layer for semiconductor elements, a pixel dividing layer for organic EL elements, a planarization layer for a TFT substrate of a display device using organic EL elements, a wiring protective insulating layer for a circuit board, a crystal-borne microlens for a solid-state imaging element, or a planarization layer for various display devices / solid-state imaging elements. For example, it can preferably be used as a surface protective layer or interlayer insulating layer for magnetoresistive random access memory (MRAM) with low heat resistance, polymer memory (Polymer Ferroelectric RAM (PFRAM)) or phase change memory (Phase Change RAM (PCRAM) or Ovonics Unified Memory (OUM)) that are expected to become next-generation memory.

[0212] <Organic EL Display Device>

[0213] The organic EL display device of the present invention includes the curing film of the present invention. The organic EL display device using the curing film of the present invention preferably includes at least a substrate, a first electrode, a second electrode, an organic EL layer, a planarization layer, and a pixel segmentation layer, wherein the curing film is contained within the planarization layer and / or the pixel segmentation layer. By including the curing film of the present invention in the planarization layer and / or the pixel segmentation layer, an organic EL display device with excellent long-term reliability can be provided.

[0214] The organic EL display device using the curing film of the present invention is an organic EL display device having multiple pixels formed on a matrix. As for the driving method of the organic EL display device, it is generally divided into a passive matrix type, in which electrodes are divided into rows and columns and only pixels sandwiched between the electrodes emit light, and an active matrix type, in which several TFTs are disposed on each pixel and switched on and off, but there is no particular limitation. The organic EL display device is formed on a substrate in the order of planarization layer, first electrode, pixel division layer, organic EL layer, and second electrode. The active matrix type organic EL display device has TFTs and a driving circuit including wiring located on the sides of the TFTs and connected to the TFTs on a substrate such as glass, and a planarization layer is provided on the driving circuit in a manner that covers the unevenness, and then an organic EL layer is provided on the planarization layer. The organic EL layer and the wiring are connected via contact holes formed in the planarization layer. Furthermore, in the organic EL display device of the embodiment of the present invention, a pixel division layer is formed on the first electrode.

[0215] Figure 1This is a cross-sectional view of an organic EL display device disposed on a substrate 1. Bottom-gate or top-gate TFTs 2 are arranged in a matrix on the substrate 1, and a TFT insulating layer 3 is formed covering the TFTs 2. Furthermore, wiring 4 connected to the TFTs 2 is disposed beneath the TFT insulating layer 3. A planarization layer 5 is disposed on the TFT insulating layer 3. Contact holes 6 are provided on the planarization layer 5, exposing the wiring 4. A first electrode 7 is formed on the planarization layer 5, connected to the wiring 4 via the contact holes 6. A pixel segmentation layer 8 is formed, covering the periphery of the first electrode 7. An organic EL layer 9 and a second electrode 10 are then formed thereon. The organic EL display device can be a top-emitting type emitting light from the opposite side of the substrate 1, or a bottom-emitting type emitting light from the substrate 1 side.

[0216] Furthermore, in the aforementioned organic EL display device, a color display can be obtained by arranging organic EL elements, each having a light emission peak wavelength, in the red, green, and blue regions as an organic EL layer, or by using a white organic EL layer applied across the entire surface in combination with a color filter. In a color display, the peak wavelengths of light displayed in the red region are typically in the range of 560 nm to 700 nm, in the green region, 500 nm to 560 nm, and in the blue region, 420 nm to 500 nm.

[0217] In organic EL elements, each portion of the area where the first and second electrodes, arranged in opposite directions, intersect and overlap, and which is defined by a pixel segmentation layer on the first electrode, is called a light-emitting pixel. The shape of the light-emitting pixel is not particularly limited; for example, it can be rectangular or circular, and can easily vary depending on the shape of the pixel segmentation layer. In active-matrix displays, sometimes the portion forming the switching element is configured to occupy a portion of the light-emitting pixel; therefore, sometimes the shape of the light-emitting pixel is not rectangular, but rather a partially missing shape.

[0218] In the fabrication of the organic EL element of this invention, an organic EL layer is formed using a mask evaporation method. The mask evaporation method is a method of patterning an organic compound by evaporating it using an evaporation mask. An evaporation mask with an opening having the desired pattern shape is placed on the evaporation source side of a substrate for evaporation. To obtain a high-precision evaporation pattern, it is important to use an evaporation mask with high flatness in close contact with the substrate. Generally, techniques such as applying tension to the evaporation mask or using a magnet positioned on the back of the substrate to ensure close contact between the evaporation mask and the substrate are used.

[0219] Methods for manufacturing vapor deposition masks with openings of the desired pattern shape include etching, mechanical grinding, sandblasting, sintering, laser processing, and the use of photosensitive resins. However, in cases where fine patterns are required, etching or electroforming methods with high processing precision are often used.

[0220] The structure of the organic EL layer contained in the organic EL element of the present invention is not particularly limited, and can be any one of (1) hole transport layer / light emission layer, (2) hole transport layer / light emission layer / electron transport layer, and (3) light emission layer / electron transport layer.

[0221] The second electrode is then formed. In active matrix type, the second electrode is usually formed as a solid throughout the light-emitting area. The second electrode is required to function as a cathode that can efficiently inject electrons; therefore, metallic materials are often used to ensure electrode stability. Alternatively, the first electrode can be used as the cathode, and the second electrode as the anode.

[0222] After the second electrode is formed, sealing is performed to obtain the organic EL display device. Generally, organic EL elements are not resistant to oxygen or moisture. To obtain a highly reliable display device, it is preferable to seal in an environment with minimal oxygen and moisture. For the components used in the sealing, components with high gas barrier properties are also preferred.

[0223] To improve the effect of reducing external light reflection, the organic EL display device of the present invention preferably further includes a color filter having a black matrix. The black matrix is ​​preferably made of resins such as epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, polyolefin resin, or siloxane resin.

[0224] The black matrix contains a colorant. As a colorant, it may contain, for example, black organic pigments, mixed organic pigments, inorganic pigments, etc. As a black organic pigment, it may contain, for example, carbon black, perylene black, aniline black, benzofuranone pigments, etc. As a mixed organic pigment, it may contain, for example, pigments that are approximately black by mixing two or more pigments such as red, blue, green, purple, yellow, magenta, and / or cyan. As a black inorganic pigment, it may contain, for example, graphite; microparticles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, etc.; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal nitrides; metal carbides, etc. Among these, carbon black, titanium nitrides, titanium carbides, or composite particles of these with metals such as silver, which have high opacity, are preferred.

[0225] The OD value of the black matrix is ​​preferably 1.5 or higher, more preferably 2.5 or higher, and even more preferably 4.5 or higher.

[0226] Display devices other than organic EL display devices

[0227] by Figure 2 Example will be used to describe another display device having the curing film of the present invention. The display device is a display device having at least metal wiring, the curing film of the present invention, and a plurality of light-emitting elements, and is configured such that: the light-emitting elements include a pair of electrode terminals on any one side, the pair of electrode terminals are connected to a plurality of metal wirings extending in the curing film, and the plurality of metal wirings are electrically insulated by the curing film.

[0228] exist Figure 2 In this display device 11, a plurality of light-emitting elements 12 are disposed on an opposing substrate 15, and a hardening film 13 is disposed on the light-emitting elements 12. Here, "on the light-emitting elements" refers not only to the surface of the light-emitting elements, but also to any part of the substrate above the light-emitting elements. Figure 2 The illustrated configuration includes a structure where multiple hardening films 13 are further stacked on a hardening film 13 disposed in contact with at least a portion of the light-emitting element 12, resulting in a total of three layers. However, the hardening film 13 may also be a single layer. The light-emitting element 12 includes a pair of electrode terminals 16 on the opposite side of the surface in contact with the opposing substrate 15, and each electrode terminal 16 is connected to a metal wiring 14 extending in the hardening film 13. Furthermore, if the multiple metal wirings 14 extending in the hardening film 13 are covered by the hardening film 13, the hardening film 13 also functions as an insulating layer, thus forming a structure that maintains electrical insulation. The term "structure that maintains electrical insulation for the metal wiring" refers to using a hardening film containing component (a) to cover the portion of the metal wiring requiring electrical insulation. Additionally, in this invention, the term "insulating layer having electrical insulation" refers to an insulating layer with a volume resistivity of 10⁻⁶. 12 The light-emitting element 12 is in a state of Ω·cm or higher. Furthermore, the light-emitting element 12 is electrically connected to the driving element 18 attached to the light-emitting element driving substrate 17 via metal wiring 14 or metal wiring 14c, thereby controlling the light emission of the light-emitting element 12. The light-emitting element driving substrate 17 is positioned opposite to the opposing substrate 15. Additionally, the light-emitting element driving substrate 17 is electrically connected to the metal wiring 14, for example, via solder bumps 20. Furthermore, to prevent the diffusion of metal from the metal wiring 14, a barrier metal 19 may be provided.

[0229] <Electronic Components>

[0230] The electronic component of the present invention is an electronic component having the curing film of the present invention. The curing film of the present invention can be used in electronic components such as semiconductor devices. Here, examples of electronic components include: active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memory, as well as passive components such as resistors, capacitors, and inductors. In addition, electronic components using semiconductors are also referred to as semiconductor devices or semiconductor packages. The semiconductor device referred to in the present invention refers to a device assembly capable of functioning by utilizing the characteristics of semiconductor elements. Electro-optical devices or semiconductor circuit boards formed by connecting semiconductor elements to a substrate, those with multiple semiconductor elements stacked, and electronic devices containing these are all included in semiconductor devices. In addition, electronic components such as interlayers for connecting semiconductor elements to a substrate are also included in semiconductor devices. Specifically, the curing film of the present invention has excellent electrical insulation, mechanical strength, adhesion, and heat resistance, and therefore can be used as surface protective films such as passivation films or buffer coating films for semiconductor elements, interlayer insulating films formed between rewiring layers on the surface of semiconductor elements, inter-element insulating films when bonding multiple semiconductor elements, and interlayer insulating films between wiring layers of multilayer wiring boards or interlayers for high-density mounting.

[0231] More preferably, a semiconductor device in which the hardening film of the present invention is configured as a surface protective film for a semiconductor or an interlayer insulating film between rewiring layers is manufactured. By configuring the hardening film of the present invention as a surface protective film for a semiconductor or an interlayer insulating film between rewiring layers, a highly reliable semiconductor device can be manufactured.

[0232] A preferred semiconductor device is one in which the rewiring and the interlayer insulating film are repeatedly arranged in two to ten layers. By repeatedly arranging the rewiring and the interlayer insulating film in two to ten layers, miniaturization of the semiconductor device can be achieved.

[0233] Furthermore, the electronic components of the present invention preferably include the curing film of the present invention on a substrate. The substrate for forming the curing film can be appropriately selected according to the application and process, and examples include: silicon substrates, silicon carbide substrates, gallium nitride substrates, ceramics, gallium arsenide, metals, epoxy resins, etc., preferably silicon substrates, silicon carbide substrates, or gallium nitride substrates, and more preferably silicon carbide substrates or gallium nitride substrates.

[0234] Example

[0235] The present invention will now be described with reference to examples, but the present invention is not limited to these examples. Furthermore, the evaluations in the examples were performed using the following methods.

[0236] (1) Electron probe microanalysis of hardened film

[0237] The varnishes obtained from the various examples and comparative examples were spin-coated onto a 5 cm square glass substrate to achieve a film thickness of 2.0 μm after heat treatment (curing). A pre-baked film was then prepared by pre-baking at 120°C for 120 seconds. Subsequently, without UV exposure, development was performed using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution to reduce the film thickness of the unexposed areas by approximately 0.5 μm. Then, a hardened film was prepared by curing in a nitrogen environment at 250°C for 60 minutes using a high-temperature cleanroom oven INH-9CD-S manufactured by Koyo Heating Systems Co., Ltd.

[0238] In addition, the thickness of the hardened film was measured using a stylus profilometer (P-15; manufactured by KLA-Tencor).

[0239] For the hardened films obtained in various ways, the cross-section of the hardened film was exposed by tilting and ion polishing. After carbon evaporation on the exposed hardened film cross-section, elemental analysis was performed using an electron probe microanalyzer JXA-8530F (manufactured by NEC Japan). The measurement conditions were set as follows: accelerating voltage: 6 kV, irradiation current: 25 nA, measurement time: 10 seconds. The Kα peak intensity of C (carbon atom) was measured at 44.00 Å using an LDE2H spectrophotometer; the Kα peak intensity of Si (silicon atom) was measured at 7.12 Å using a PETH spectrophotometer; the Kα peak intensity of N (nitrogen atom) was measured at 31.60 Å using an LDE1 spectrophotometer; the Kα peak intensity of O (oxygen atom) was measured at 23.71 Å using an LDE1 spectrophotometer; and the Kα peak intensity of F (fluorine atom) was measured at 18.31 Å using an LDE1 spectrophotometer. BaSO4, SiO2, AlN, CaF2, and SiC were used as standard samples for each element, and ZAF correction (Z: atom numbering correction, A: absorption correction, F: fluorescence excitation correction) was applied. Each sample was measured three times, and the molar percentage of each element in the hardened film was calculated based on the average value. The molar ratio of fluorine atoms to carbon atoms (F / C ratio) and the molar ratio of silicon atoms to carbon atoms (Si / C ratio) were then calculated.

[0240] (2) Evaluation of reprocessability during the production of hardened film

[0241] The developed glass substrate with resin film, prepared in the same manner as in (1), was immersed in propylene glycol monomethyl ether and left at room temperature for 30 minutes. Afterward, the glass substrate was removed from the propylene glycol monomethyl ether and visually inspected for any residue. If no residue was found on the glass substrate, it was classified as "A"; if a small amount of residue was found on the glass substrate, it was classified as "B"; and if a large amount of residue was found on the glass substrate, it was classified as "C".

[0242] (3) Evaluation of the bending resistance of the hardened film

[0243] The varnish obtained from each example and comparative example was spin-coated onto a polyimide film substrate to achieve a film thickness of 2.0 μm after heat treatment (curing). A pre-baked film was then prepared by pre-baking at 120°C for 120 seconds. Subsequently, without UV exposure, development was performed using a 2.38% TMAH aqueous solution to reduce the film thickness of the unexposed areas by approximately 0.5 μm. Then, a hardened film was prepared by curing in a nitrogen environment at 250°C for 60 minutes using a high-temperature cleanroom oven INH-9CD-S manufactured by Koyo Heating Systems Co., Ltd.

[0244] Next, ten polyimide film substrates, including the hardened film, were cut into pieces measuring 50 mm x 10 mm. Then, with the hardened film side facing outwards, the polyimide film substrate was bent along a 25 mm longitudinal line with a radius of curvature ranging from 0.1 mm to 1.0 mm, and held in this position for 30 seconds. After 30 seconds, the bent polyimide film substrate was restored to its original shape, and the bending portion along the 25 mm longitudinal line on the surface of the hardened film was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and the changes in the appearance of the hardened film surface were evaluated. Bending tests were conducted by varying the radius of curvature within the range of 0.1 mm to 1.0 mm, and the minimum radius of curvature at which no peeling of the hardened film from the polyimide film substrate or cracks in the hardened film surface occurred was recorded. If the minimum radius of curvature is less than 0.2 mm, it is judged as "S"; if the minimum radius of curvature is 0.2 mm or more but less than 0.4 mm, it is judged as "A"; if the minimum radius of curvature is 0.4 mm or more but less than 0.6 mm, it is judged as "B"; and if the minimum radius of curvature is 0.6 mm or more, it is judged as "C".

[0245] (4) Calculation of the content of β-alkoxypropionamide in the hardened film

[0246] Ten mg of a hardened membrane prepared using the same method as in (1) was collected, and the component containing β-alkoxypropionamide was adsorbed and captured by a purge and trap method. Specifically, the collected hardened membrane was heated at 400°C for 60 minutes using helium as the purge gas, and the component detached from the hardened membrane was captured into the adsorption tube. The captured component was heated at 320°C for 5 minutes to detach it from the adsorption tube, and GC-MS analysis was performed using a GC-MS apparatus 7890 / 5975C (manufactured by Agilent Technologies) under the following conditions: column temperature: 40°C to 300°C, carrier gas: helium (1.5 mL / min), and scan range: m / Z 29 to 600. β-alkoxypropionamide, the same as the detected β-alkoxypropionamide, was used as a standard substance, and GC-MS analysis was performed under the same conditions to generate a calibration curve, thereby calculating the amount of β-alkoxypropionamide gas produced. Based on the calculated amount of β-alkoxypropionamide gas produced and the mass of the sample used for measurement, the content (mass%) of β-alkoxypropionamide in the hardened film can be calculated.

[0247] (5) Long-term reliability evaluation of organic EL display devices (brightness evaluation under high temperature continuous driving)

[0248] A schematic diagram of the manufacturing process of an organic EL display device is shown below. Figure 3 First, on a 38 mm × 46 mm alkali-free glass substrate 21, an ITO transparent conductive film of 10 nm is formed on the entire surface of the substrate by sputtering. Then, it is etched into the desired shape to form a first electrode (transparent electrode) 22. Additionally, an auxiliary electrode 23 for removing the second electrode is also formed. Figure 3(1) The obtained electrode-bearing substrate was ultrasonically cleaned for 10 minutes using Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.), followed by rinsing with ultrapure water. Next, the photosensitive resin compositions obtained in each example and comparative example were coated onto the entire surface of the substrate by spin coating and pre-baked on a heated plate at 120°C for 2 minutes. For the obtained pre-baked film, a photomask with the desired pattern was exposed to the minimum exposure of each photosensitive resin composition using a high-pressure mercury lamp as the light source, and then developed using a 2.38% by mass TMAH aqueous solution to dissolve the unwanted parts and rinse with pure water to obtain the resin pattern. The obtained resin pattern was then heat-treated at 230°C for 60 minutes in an atmospheric or nitrogen environment using a high-temperature clean oven INH-9CD-S manufactured by Koyo Heating Systems Co., Ltd., and hardened. Thus, a pixel segmentation layer 24 is formed within the effective area of ​​the substrate. The pixel segmentation layer 24 has openings with a width of 70 μm and a length of 260 μm arranged at intervals of 155 μm in the width direction and 465 μm in the length direction, with each opening exposing the first electrode. In this way, a pixel segmentation layer with an aperture ratio of 25% is formed within the effective area of ​​the substrate, which is a quadrilateral with one side measuring 16 mm. The thickness of the pixel segmentation layer is approximately 1.5 μm. Figure 3 (2)).

[0249] Next, an organic EL layer 25 containing a light-emitting layer is formed on the substrate on which the pixel segmentation layer is formed by vacuum evaporation. Furthermore, the vacuum level during evaporation is 1×10⁻⁶. -3 Below Pa, the substrate is rotated relative to the evaporation source during the evaporation process. First, a 10 nm layer of compound (HT-1) is deposited as a hole injection layer, and a 50 nm layer of compound (HT-2) is deposited as a hole transport layer. Next, as the light-emitting layer, a compound (GH-1) as the host material and a compound (GD-1) as the dopant material are deposited to a thickness of 40 nm at a doping concentration of 10%. Next, a compound (ET-1) as the electron transport material and a compound (LiQ) are stacked at a volume ratio of 1:1 to a thickness of 40 nm. Thus, an organic EL layer 25 comprising a hole injection layer / hole transport layer / light-emitting layer / electron transport layer is formed. Figure 3 (3) The structure of the compound used in the organic EL layer is shown below.

[0250] [Chemistry 19]

[0251]

[0252] Next, after depositing 2 nm of compound (LiQ), Mg and Ag were deposited at a volume ratio of 10:1 for 10 nm as the second electrode (non-transparent electrode). Figure 3 (4) Finally, by sealing the cap-shaped glass plate using an epoxy resin adhesive in a low-humidity nitrogen environment, four top-emitting organic EL display devices with four sides of 5 mm were fabricated on a substrate. Furthermore, the film thickness mentioned here refers to the display value in a crystal oscillating film thickness monitor.

[0253] Using the method described above, at 10 mA / cm 2 The fabricated organic EL display device was DC driven, and the initial brightness was measured. Next, it was tested at 85°C with a current of 10 mA / cm². 2 The same organic EL display device was continuously driven by DC, and the time it took for the brightness to decrease from the initial brightness to half was measured as the brightness halving time. Cases with a brightness halving time of 400 hours or more were classified as "S", cases with a brightness halving time of 380 hours or more but less than 400 hours were classified as "A", cases with a brightness halving time of 360 hours or more but less than 380 hours were classified as "B", and cases with a brightness halving time of less than 360 hours were classified as "C".

[0254] (6) Evaluation of light-blocking properties at 450 nm (transmittance at 450 nm)

[0255] For the hardened film prepared using the same method as (1), the transmittance spectrum of light with wavelengths from 300 nm to 800 nm was measured using a MultiSpec-1500 UV-Vis spectrophotometer (manufactured by Shimadzu Corporation), and the transmittance of light with a wavelength of 450 nm at a film thickness of 2.0 μm after curing was determined.

[0256] Furthermore, when the thickness of the hardened film is greater than 2.0 μm, the transmittance is converted to absorbance, corrected to absorbance at a film thickness of 2.0 μm, and then the absorbance is converted back to transmittance. Thus, the transmittance at a wavelength of 450 nm at a film thickness of 2.0 μm is obtained.

[0257] (7) Evaluation of visible light blocking property (OD value per 1 μm)

[0258] For the hardened film made in the same manner as (1), the OD value was measured using an optical density meter (361T; manufactured by X-Rite). The OD value per 1 μm (hereinafter referred to as OD / μm) was obtained by dividing the obtained OD value by the thickness of the hardened film. (OD value per 1 μm = OD value / thickness of hardened film)

[0259] Synthetic Example 1: Synthesis of a quinone diazide compound (c-1)

[0260] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of 5-naphthoquinone diazidesulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. 15.18 g of triethylamine, mixed with 50 g of 1,4-dioxane, was added dropwise to the mixture in a manner that prevented the system temperature from exceeding 35°C. The mixture was stirred at 30°C for 2 hours after the addition. The triethylamine salt was removed by filtration, and the resulting filtrate was added to water. The precipitate was collected by filtration. The precipitate was dried using a vacuum dryer to obtain the quinone diazide compound represented by the following formula (c-1).

[0261] [Chemistry 20]

[0262]

[0263] Synthesis Example 2: Synthesis of Polyhydroxystyrene (p-1)

[0264] In a mixture of 2400 g of tetrahydrofuran and 2.56 g (0.04 mol) of sec-butyllithium as an initiator, 105.75 g (0.6 mol) of p-tert-butoxystyrene was added. The mixture was stirred and allowed to polymerize for 3 hours. Then, 12.82 g (0.4 mol) of methanol was added to stop the polymerization. Next, to purify the polymer, the reaction mixture was injected into 3 L of methanol, and the precipitated polymer was dried. The obtained polymer was dissolved in 1.6 L of acetone, and 2 g of concentrated hydrochloric acid was added at 60 °C with stirring for 7 hours to deprotect the p-tert-butoxy group, converting p-tert-butoxystyrene to hydroxystyrene. After the reaction was complete, the solution was injected into water to precipitate the polymer. The precipitate was washed three times with water and then dried in a vacuum dryer at 50 °C for 24 hours to obtain the target polyhydroxystyrene (p-1).

[0265] Synthesis Example 3: Synthesis of diamine compound (α)

[0266] Dissolve 18.3 g (0.05 mol) of 6FAP in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cool to -15 °C. Add dropwise a solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone. After the addition is complete, react at -15 °C for 4 hours, then allow to return to room temperature. Filter the precipitated white solid and dry it under vacuum at 50 °C.

[0267] 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve. 2 g of 5% palladium-carbon was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. The reaction was considered complete after approximately 2 hours, when the balloon was confirmed to have stopped shrinking. After the reaction, the palladium compound acting as a catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a diamine compound (α) containing fluorine atoms, as represented by the following formula.

[0268] [Chemistry 21]

[0269]

[0270] Synthesis Example 4: Synthesis of diamine compound (β)

[0271] 25.66 g (0.086 mol) of 4,4'-(2-ethylhexylene)diphenol and 100 ml of glacial acetic acid were added to a 500 ml four-necked flask containing a stirrer, thermocouple, and dropping funnel, and the mixture was stirred. The internal temperature was raised to 50 °C using a hot water bath. 2 ml (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour, followed by cooling in an ice bath to lower the internal temperature to 13 °C. Then, 13.3 ml (0.149 mol) of concentrated nitric acid was added dropwise over another 1 hour. The mixture was then stirred continuously for 3 hours. The precipitated yellow crystals were collected by filtration, washed sequentially with 40 ml of glacial acetic acid and 80 ml of deionized water, and dried under reduced pressure to obtain the dinitrocellulose.

[0272] Subsequently, 52.44 g (0.135 mol) of the dinitromatrix, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were added to a 2 L four-necked flask containing a stirrer, thermocouple, Dimroth cooling tube, and dropping funnel. The mixture was stirred under ice bath cooling, and 0.9 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) suspended in 30 ml of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, washed with 300 ml of ethanol, and the palladium-carbon was removed by filtration. All solvent was removed by heating under reduced pressure. The residue was washed with 75 ml of ice-bath cooled ethanol and filtered, followed by washing with 75 ml of deionized water and 150 ml of diethyl ether, and then dried under reduced pressure to obtain diamine (β).

[0273] [Chemistry 22]

[0274]

[0275] Synthesis Example 5: Synthesis of diamine compound (γ)

[0276] The diamine compound (β) obtained in Synthesis Example 4 was used instead of 6FAP, and the diamine compound (γ) was otherwise obtained in the same manner as in Synthesis Example 3.

[0277] [Chemistry 23]

[0278]

[0279] Synthesis Example 6: Synthesis of diamine compound (δ)

[0280] The dinitro compound was synthesized using 26.70 g (0.086 mol) of 4,4'-(3,3,5-trimethylcyclohexylene)bisphenol instead of 4,4'-(2-ethylhexylene)diphenol, and the diamine compound (δ) was obtained using 54.06 g (0.135 mol) of dinitro compound, otherwise the same as in Synthesis Example 4.

[0281] [Chemistry 24]

[0282]

[0283] Synthesis Example 7: Synthesis of Alkali-Soluble Resin (a-1)

[0284] Under a dry nitrogen stream, 31.02 g (0.10 mol) of ODPA was dissolved in 500 g of MPA. 21.96 g (0.085 mol) of BAP and 1.24 g (0.005 mol) of SiDA were added together with the MPA, and the mixture was reacted at 40°C for 2 hours. Next, 2.18 g (0.02 mol) of 3-aminophenol as a capping agent was added together with 5 g of MPA, and the mixture was reacted at 50°C for 2 hours. Then, a solution prepared by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal with 50 g of MPA was added. After addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3 L of water to obtain a white precipitate. The precipitate obtained by filtration was washed three times with water and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide precursor (a-1) for use as an alkali-soluble resin.

[0285] Synthesis Example 17: Synthesis of Alkali-Soluble Resin (a-11)

[0286] Under a dry nitrogen stream, 12.92 g (0.050 mol) of BAP, 12.82 g (0.035 mol) of 6FAP, 1.24 g (0.005 mol) of SiDA, 2.18 g (0.02 mol) of MAP, and 52.8 g (0.6 mol) of glycidyl methyl ether were dissolved in 500 g of MPA, and the solution was cooled to -15°C. A solution containing 29.51 g (0.10 mol) of OBBC dissolved in 50 g of MPA was added dropwise, keeping the internal temperature below 0°C. After the addition was complete, the mixture was stirred continuously at -15°C for 6 hours. After the reaction was complete, the solution was added to 3 L of water containing 10% by weight methanol to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80°C for 24 hours to obtain polybenzoxazole precursor (a-11) as an alkali-soluble resin.

[0287] Synthesis Examples 8 to 16, Synthesis Examples 18 to 25, Comparative Synthesis Examples 1 to 4

[0288] As described in Table 1, the amine composition, acid composition, and polymerization solvent were changed, and otherwise obtained in the same manner as in Synthesis Example 7, polyimide precursors (a-2) to (a-10), (a-12) to (a-19), and (a'-1) to (a'-4).

[0289] Comparative Synthesis Example 5

[0290] As described in Table 1, the amine composition, acid composition, and polymerization solvent were changed, otherwise the polybenzoxazole precursor (a'-5) was obtained in the same manner as in Synthesis Example 17.

[0291] The names of the compounds used in each example and comparative example are shown below. Compounds other than commercially available products were synthesized using existing methods.

[0292] GBL: γ-Butyrolactone

[0293] MPA: 3-Methoxy-N,N-Dimethylpropionamide

[0294] NMP: N-methylpyrrolidone

[0295] BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane (a diamine without fluorine atoms)

[0296] ABPS: Bis(3-amino-4-hydroxyphenyl) sulfone (a diamine without fluorine atoms)

[0297] BAHF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (a diamine without fluorine atoms and possessing a fluorene structure)

[0298] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane (a diamine containing silicon atoms but without fluorine atoms)

[0299] 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (a diamine containing a fluorine atom)

[0300] 8FBZ: 4,4'-Diaminooctafluorobiphenyl (a diamine containing a fluorine atom directly bonded to the sp2 carbon)

[0301] MAP: 3-Aminophenol

[0302] ODPA: 3,3',4,4'-Diphenyl ether tetracarboxylic acid dianhydride (an acid dianhydride that does not contain a fluorine atom)

[0303] TDA: Tetrahydronaphthalene dianhydride (an acid dianhydride that does not contain fluorine atoms but has an alicyclic structure)

[0304] 6FDA: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (an acid dianhydride containing a fluorine atom)

[0305] OBBC: Diphenyl ether dicarboxylic acid dichloride (acyl chloride without fluorine atoms)

[0306] b-1: 1,2,4-Trihydroxybenzene (an aromatic hydrocarbon compound having at least three phenolic hydroxyl groups within an aromatic ring).

[0307] b'-1: 1,1,1-Tris(4-hydroxyphenyl)ethane

[0308] BTS: Butyl p-toluenesulfonate (a thermal acid generator that produces specific sulfonic acids and / or sulfonate ions during heat treatment).

[0309] s-1: 3-glycidoxypropyltrimethoxysilane (silane coupling agent)

[0310] e-1: The thermal crosslinking agent represented by the structure shown below

[0311] e-2: The thermal crosslinking agent represented by the structure shown below

[0312] d1-1: The dye represented by the structure shown below

[0313] d1-2: Dyes represented by the structures shown below

[0314] [Chemistry 25]

[0315]

[0316] Example 1

[0317] 10.0 g of polyimide precursor (a-1), 2.0 g of photosensitive compound (c-1), and 2.0 g of (e-1) were dissolved in 50 g of GBL and filtered using a 0.2 μm polytetrafluoroethylene filter to obtain varnish A-1 of the positive photosensitive resin composition. The obtained varnish A-1 was used for the following tests as described: electron probe microanalysis of the hardened film, evaluation of the reprocessability during hardened film fabrication, evaluation of the flexural strength of the hardened film, calculation of the β-alkoxypropionamide content in the hardened film, evaluation of the long-term reliability of the organic EL display device, evaluation of the 450 nm light-blocking property, and evaluation of the visible light-blocking property.

[0318] The hardened membrane contains one or more compounds derived from quinone diazide compounds (c-1), specifically selected from the group consisting of carboxylic acids containing an indene structure, carboxylic acid esters containing an indene structure, sulfonic acids containing an indene structure, and aryl sulfonates containing an indene structure. It can be confirmed by analyzing the hardened membrane using methods such as proton nuclear magnetic resonance spectrometry, infrared spectroscopy, thermal decomposition gas chromatography, reactive thermal decomposition gas chromatography, liquid chromatography, and time-of-flight secondary ion chromatography.

[0319] Examples 2 to 33, Comparative Examples 1 to 5

[0320] As described in Tables 2 and 3, components (a), (b), (c), other components, and solvents were modified, and a varnish of the photosensitive resin composition was obtained in the same manner as in Example 1. The obtained varnish was used for electron probe microanalysis of the hardened film, evaluation of the reprocessability during hardened film production, evaluation of the flexural strength of the hardened film, calculation of the β-alkoxypropionamide content in the hardened film, evaluation of the long-term reliability of the organic EL display device, evaluation of the 450 nm light-blocking property, and evaluation of the visible light light-blocking property. The compounds derived from the quinone diazide compound (c-1) in the hardened film were the same as in Example 1.

[0321] [Table 1]

[0322]

[0323] [Table 2-1]

[0324]

[0325] [Table 2-2]

[0326]

[0327] [Table 2-3]

[0328]

[0329] [Table 2-4]

[0330]

[0331] [Table 3]

[0332]

[0333] Explanation of icon numbers

[0334] 1: Substrate

[0335] 2: TFT

[0336] 3: TFT insulating layer

[0337] 4: Wiring

[0338] 5: Planarization layer

[0339] 6: Contact hole

[0340] 7: First electrode

[0341] 8: Pixel segmentation layer

[0342] 9: Organic EL layer

[0343] 10: Second electrode

[0344] 11: Display device

[0345] 12: Light-emitting element

[0346] 13: Hardened film

[0347] 14, 14c: Metal wiring

[0348] 15: Opposing substrates

[0349] 16: Electrode terminals

[0350] 17: Light-emitting element driving substrate

[0351] 18: Driving element

[0352] 19: Barrier Metal

[0353] 20: Solder bump

[0354] 21: Alkali-free glass substrate

[0355] 22: First electrode (transparent electrode)

[0356] 23: Auxiliary electrode

[0357] 24: Pixel Segmentation Layer

[0358] 25: Organic EL layer

[0359] 26: Second electrode (non-transparent electrode)

Claims

1. A hardened film comprising polyimide and / or polybenzoxazole, wherein in the hardened film, When the profile of the hardened film was measured using an electron probe microanalyzer, the molar ratio of fluorine atoms to carbon atoms, F (fluorine atoms) / C (carbon atoms), was greater than 0 and less than 0.

05.

2. The hardened film according to claim 1 further comprises one or more compounds selected from the group consisting of carboxylic acids containing an indene structure, carboxylic acid esters containing an indene structure, sulfonic acids containing an indene structure, and aryl sulfonates containing an indene structure.

3. The hardened film according to claim 1 or 2 further comprises polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer.

4. The hardened film according to claim 1 or 2 further comprises an aromatic hydrocarbon compound having at least three phenolic hydroxyl groups within an aromatic ring.

5. The hardened film according to claim 1 or 2 further contains β-alkoxypropionamide.

6. The hardened membrane according to claim 1 or 2, further comprising one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5), or sulfonate ions derived from one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5): [Chemistry 1] In equation (3), R 5 Each of the following independently represents a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, where n represents an integer from 1 to 5; in equation (4), R 6 A monovalent organic group representing 1 to 10 carbon atoms.

7. The hardened film according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole has repeating units comprising an acid component and an amine component. With the acid and amine components in all repeating units set to 100 mol%, the total of acid components with fluorene structures and amine components with fluorene structures in the total of 200 mol% is between 0 mol% and 50 mol%.

8. The hardened membrane according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole has residues represented by formula (6): [Chemistry 2] In equation (6), X 1 Let X represent the direct bond, the divalent base represented by equation (7), or the divalent base represented by equation (8) independently. 2 The divalent base represented by equation (9) or equation (10), R 8 Each of the following can be used to independently represent an alkyl group or a hydroxyl group having 1 to 4 carbon atoms, and each of the following can be used to independently represent an integer from 0 to 4. [Chemistry 3] In equations (7) and (8), R 9 Each of the following can independently represent an alkyl group or a hydroxyl group having 1 to 4 carbon atoms, and e can independently represent an integer from 0 to 4. In expression (6) , Indicates the bond node that is bonded to the aromatic ring; [Chemistry 4] In equations (9) and (10), R 11 Each of the alkyl groups having 1 to 4 carbon atoms is represented independently, R 12 and R 13 Each can independently represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. The terminator represents the bond node with the aromatic ring; f represents an integer from 1 to 4 independently, and g represents 1 or 2; where, R 12 With R 13 Indicates different substituents.

9. The hardened film according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole has repeating units comprising an acid component and an amine component. With the acid and amine components in all repeating units set to 100 mol%, the total of acid and amine components in the total of 200 mol% is between 0 mol% and 40 mol%.

10. The hardened film according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole comprises repeating units having fluorine atoms directly bonded to sp2 carbons.

11. The hardened film according to claim 10, wherein the polyimide and / or polybenzoxazole has repeating units comprising an acid component and an amine component. With the acid and amine components in all repeating units set to 100 mol%, the total of the acid and amine components in the total of 200 mol% is between 5 mol% and 100 mol%.

12. The hardened film according to claim 1 or 2, wherein the molar ratio of silicon atoms to carbon atoms, Si (silicon atoms) / C (carbon atoms), obtained by measuring the cross-section of the hardened film using an electron probe microanalyzer, is 0.001 or more and 0.005 or less.

13. The hardened film according to claim 1 or 2, wherein the transmittance of light with a wavelength of 450 nm at a film thickness of 2.0 μm is less than 30%.

14. The hardened film according to claim 1 or 2, wherein the optical density under visible light is 0.5 to 1.5 per 1 μm film thickness.

15. An organic electroluminescent display device having a hardened film as described in claim 1 or 2.

16. The organic electroluminescent display device according to claim 15, further comprising a color filter containing a black matrix.

17. An electronic component having a hardened film as described in claim 1 or 2.

Images