Organic EL display device, method for manufacturing the same, and method for manufacturing a cured product

Abstract

An object of the present invention is to provide an organic EL display device that does not cause a decrease in luminance or pixel shrinkage and has excellent long-term reliability. The present invention is an organic EL display device comprising a cured product of a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinone diazide sulfonic acid ester compound, wherein the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the cured product is set to 1. (S) , the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon and sulfur is set to I (TOTAL) When the intensity ratio I (S) / I (TOTAL) Alternatively, the present invention is a method for producing the above-mentioned cured product.

Description

Technical Field

[0001] The present invention relates to an organic EL display device, a method for producing a cured product, and a method for producing an organic EL display device. Background Art

[0002] Among display devices having thin displays such as mobile phones, tablet PCs, and televisions, a large number of products using organic electroluminescence (hereinafter referred to as "organic EL") display devices have been developed.

[0003] Typically, an organic EL display device comprises a driving circuit, a planarization layer, a first electrode, a pixel segmentation layer, an organic EL layer, and a second electrode on a substrate. Light is emitted by applying a voltage or flowing a current between the opposing first and second electrodes. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are commonly used as materials for the planarization layer and the pixel segmentation layer.

[0004] Meanwhile, demands for higher reliability in organic EL display devices are becoming increasingly stringent. Planarization layer materials and pixel segmentation layer materials are also required to exhibit no decrease in luminance or pixel shrinkage, even after reliability testing under accelerated conditions such as high temperature, high humidity, and light irradiation. Pixel shrinkage refers to a phenomenon in which luminance decreases at the ends of a pixel or the pixel becomes incapable of lighting.

[0005] Examples of positive-type photosensitive resin compositions proposed so far include those in which a naphthoquinone diazide sulfonic acid ester compound, a photosensitive component, is mixed with an alkali-soluble resin and a polyimide precursor is used as the resin (see, for example, Patent Document 1), and those using a polybenzoxazole precursor (see, for example, Patent Document 2). Furthermore, there has been a proposal to improve long-term reliability by controlling the sulfur concentration in the cured film within a certain range (see, for example, Patent Document 3).

[0006] Prior art literature

[0007] Patent Literature

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

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

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

[0011] Problems to be solved by the invention

[0012] However, it is difficult to say that the materials proposed in the aforementioned patent documents have sufficient performance for applications requiring higher reliability, such as in-vehicle displays. In view of the above problems, an object of the present invention is to provide an organic EL display device that does not cause a decrease in luminance or pixel shrinkage and has excellent long-term reliability.

[0013] Means for solving problems

[0014] The present invention provides an organic EL display device comprising a cured product of a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinone diazide sulfonic acid ester compound, wherein the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the cured product is set to 1. (S) (Unit: counts), the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) (Unit: counts), the intensity ratio I (S) / I (TOTAL) It is greater than 0.0001 and less than 0.008.

[0015] Alternatively, the present invention is a method for producing a cured product, which is a method for producing a cured product of a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinonediazidesulfonic acid ester compound, the method comprising: applying the photosensitive resin composition to a substrate to form a photosensitive resin film; drying the photosensitive resin film; exposing the dried photosensitive resin film; developing the exposed photosensitive resin film; and heating the developed photosensitive resin film to obtain a cured product, wherein the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the cured product is set to 1. (S) (Unit: counts), the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) (Unit: counts), the intensity ratio I (S) / I (TOTAL) It is greater than 0.0001 and less than 0.008.

[0016] Effects of the Invention

[0017] The organic EL display device of the present invention does not cause a decrease in luminance or shrinkage of pixels, and can be an organic EL display device with excellent long-term reliability. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] [ Figure 1 ] is a cross-sectional view of the TFT substrate.

[0019] [ Figure 2] is a schematic diagram of a substrate of an organic EL display device. DETAILED DESCRIPTION

[0020] Embodiments of the present invention will be described in detail.

[0021] The organic EL display device of the embodiment of the present invention is an organic EL display device having a plurality of pixels formed on a matrix. As driving methods of the organic EL display device, there are roughly two types: a passive matrix type in which electrodes are divided into columns and rows, and only pixels sandwiched between the electrodes are illuminated; and an active matrix type in which a plurality of TFTs are provided in each pixel for switching, without particular limitation. The organic EL display device has a planarization layer, a first electrode, a pixel segmentation layer, an organic EL layer, and a second electrode formed on a substrate in this order. The active matrix type organic EL display device has TFTs (thin film transistors) and wiring located on the side of the TFTs and connected to the TFTs on a substrate such as glass, a planarization layer on its driving circuit in a manner covering the concave and convex, and an organic EL element is further provided on the planarization layer. The organic EL element and the wiring are connected via contact holes formed in the planarization layer. In addition, in the organic EL display device of the embodiment of the present invention, a pixel segmentation layer is formed on the first electrode.

[0022] Figure 1 A cross-sectional view of an organic EL display device provided on a substrate 1 is shown. On the substrate 1, bottom-gate or top-gate TFTs 2 are arranged in a matrix, and a TFT insulating layer 3 is formed to cover the TFTs 2. In addition, wiring 4 connected to the TFTs 2 is provided below the TFT insulating layer 3. Furthermore, contact holes 7 opening the wirings 4 are provided on the TFT insulating layer 3, and a planarization layer 5 is provided to bury them. An opening is provided in the planarization layer 5 so as to reach the contact holes 7 of the wirings 4. In addition, a first electrode 7 is formed on the planarization layer 5 so as to be connected to the wirings 4 via the contact holes 7. In addition, a pixel segmentation layer 8 is formed to cover the periphery of the first electrode 7. Furthermore, an organic EL layer 9 and a second electrode 10 are formed thereon. This organic EL display device can be a top emission type in which light is emitted from the side opposite to the substrate 1, or a bottom emission type in which light is extracted from the substrate 1 side.

[0023] In addition, a device in which organic EL elements having peak emission wavelengths in the red, green, and blue regions are arranged on the substrate, or a device in which white organic EL elements are made on the entire surface and used in combination with a color filter is called a color display. Usually, the peak wavelength of light displayed in the red region is in the range of 560 to 700 nm, in the green region is in the range of 500 to 560 nm, and in the blue region is in the range of 420 to 500 nm.

[0024] The area referred to as a "luminescent pixel" is the area where the opposing first and second electrodes intersect and overlap, and is defined by the pixel partition layer on the first electrode. In active matrix displays, the portion forming the switching mechanism sometimes occupies a portion of the luminescent pixel, and the shape of the luminescent pixel may not be rectangular, but may be partially obscured. However, the shape of the luminescent pixel is not limited to this; for example, it can be circular, and can be easily varied depending on the shape of the pixel partition layer.

[0025] The organic EL element of the present invention is produced by forming the organic EL layer using a masked evaporation method. Masked evaporation refers to a method in which an organic compound is deposited using a deposition mask to form a pattern. Deposition is performed by placing a deposition mask with openings in the desired pattern on the deposition source side of a substrate. To achieve a highly precise deposition pattern, it is important to ensure a highly flat deposition mask adheres closely to the substrate. Common methods include applying tension to the deposition mask and using magnets placed on the back of the substrate to secure the deposition mask to the substrate.

[0026] Methods for producing a vapor deposition mask include etching, mechanical polishing, sandblasting, sintering, laser processing, and the use of photosensitive resins. However, when fine patterns need to be formed, etching and electroforming, which are excellent in processing accuracy, are often used.

[0027] The structure of the organic EL layer included in the organic EL element of the present invention is not particularly limited, and may be, for example, any of (1) hole transport layer / light-emitting layer, (2) hole transport layer / light-emitting layer / electron transport layer, and (3) light-emitting layer / electron transport layer.

[0028] Next, the second electrode is formed. For active-matrix luminescent devices, the second electrode is often formed across the entire light-emitting area. Because the second electrode is required to function as a cathode, efficiently injecting electrons, it is often made of a metal material for stability. It should be noted that the first electrode can also serve as a cathode and the second electrode as an anode.

[0029] After forming the second electrode, sealing is performed to obtain an organic EL display device. Organic EL elements are generally considered to be vulnerable to oxygen and moisture. To achieve a highly reliable display device, sealing is preferably performed in an atmosphere with minimal oxygen and moisture. The sealing member is also preferably selected to have high gas barrier properties.

[0030] The organic EL display device of the present invention is an organic EL display device comprising a cured product of a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinone diazide sulfonic acid ester compound, wherein the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the cured product is set to 1.(S) (Unit: counts), the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) (Unit: counts), the intensity ratio I (S) / I (TOTAL) It is greater than 0.0001 and less than 0.008.

[0031] The inventors of this application have conducted repeated and in-depth research and have discovered that sulfur atoms contained in the cured film are a factor that reduces the long-term reliability of organic EL devices. More specifically, they have confirmed that sulfur components in the planarization layer or pixel segmentation layer vaporize and penetrate into the interior of the pixel, causing the luminous brightness to decrease from the end of the pixel or even prevent the pixel from lighting up, a phenomenon known as pixel shrinkage. The pixel segmentation layer is in contact with the pixel end, and pixel shrinkage occurs due to the vaporized sulfur components seeping into the pixel during long-term reliability testing. In addition, although the planarization layer does not contact the pixel end, during long-term reliability testing, vaporized sulfur components pass through the area in contact with the pixel segmentation layer and move into the pixel segmentation layer, and then seep into the pixel, thereby causing pixel shrinkage.

[0032] To address this problem, the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the solidified material was set to 1. (S) The sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) When the intensity ratio I (S) / I (TOTAL) The intensity ratio is 0.008 or less, preferably 0.006 or less, more preferably 0.005 or less, further preferably 0.004 or less, and particularly preferably 0.003 or less, thereby preventing a decrease in luminance or shrinkage of pixels and providing sufficient long-term reliability as an organic EL display device. (S) / I (TOTAL) It is preferably 0.0001 or more, and more preferably 0.0005 or more.

[0033] Here, in order to obtain I (S) / I (TOTAL) The cured product having a carbon-sulfur bond of 0.008 or less can be reduced by removing sulfur dioxide from the cured product by cleavage of the carbon-sulfur bond of the naphthoquinonediazidesulfonic acid ester compound (B) during the heat treatment step.

[0034] As a method for obtaining I (S) / I (TOTAL) Specific methods for producing a cured product having a viscosity of 0.008 or less include the following methods.

[0035] [Method 1]

[0036] A method for producing a cured product of the photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinonediazidesulfonate compound, wherein the photosensitive resin composition contains (B1) a naphthoquinonediazide-4-sulfonate compound as the (B) naphthoquinonediazidesulfonate compound, wherein the step of irradiating the photosensitive resin film with ultraviolet light is performed between the step of developing the photosensitive resin film and the step of heat-treating the photosensitive resin film, and the maximum heating temperature in the step of heat-treating to obtain the cured product is set to 400° C. or higher.

[0037] [Method 2]

[0038] A method of producing a cured product of the photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinonediazidesulfonate compound, wherein the (B) naphthoquinonediazidesulfonate compound comprises only a naphthoquinonediazide-5-sulfonate compound and further comprises (C) an alkali generator, wherein the maximum heating temperature in the step of heat-treating the cured product to obtain the cured product is set to 400° C. or higher;

[0039] [Method 3]

[0040] A method for producing a cured product of a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinonediazidesulfonate compound, wherein the (B) naphthoquinonediazidesulfonate compound includes (B1) a naphthoquinonediazide-4-sulfonate compound, and further comprising (C) an alkali generator, wherein the maximum heating temperature in the step of heat-treating the cured product to obtain the cured product is set to 230°C or higher.

[0041] In any of the above methods 1 to 3, the heat treatment step allows for the removal of sulfur dioxide from the cured product by cleaving the carbon-sulfur bond of the naphthoquinonediazidesulfonic acid ester compound (B), thereby reducing the amount of sulfur atoms contained in the cured product. Of these, method 3 is most preferred because the heat treatment temperature is relatively low, thus avoiding the effects of thermal degradation of the TFT element.

[0042] The organic EL display device of the present invention preferably comprises at least a substrate, a first electrode, a second electrode, an organic EL layer, a planarization layer, and a pixel segmentation layer, wherein the cured product is contained in the planarization layer and / or the pixel segmentation layer. By incorporating the cured product into the planarization layer and / or the pixel segmentation layer, an organic EL display device with excellent long-term reliability can be provided.

[0043] Here, the time-of-flight secondary ion mass spectrometry method of the solidified material will be described in detail.

[0044] Time-of-flight secondary ion mass spectrometry is commonly referred to as TOF-SIMS (Time-Of-Flight Secondary Ion Spectrometry). TOF-SIMS is an analytical method in which pulsed primary ions are irradiated onto the surface of a solid sample in a high vacuum. The secondary ions emitted from the solid are mass-separated using a velocity distribution corresponding to their mass, with light ions having high velocities and heavy ions having low velocities. By measuring this time-of-flight distribution, a mass spectrum of the sample's outermost surface can be obtained. In this TOF-SIMS analysis, a sputtering ion gun is used to perform TOF-SIMS analysis while sputtering in the depth direction, thereby obtaining a depth-wise mass spectrum.

[0045] Next, the analysis site of the solidified material will be described. The negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the solidified material is set as I (S) , the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon and sulfur is set to I (TOTAL) , which refers to the mass spectrum information obtained by TOF-SIMS analysis of a place 500nm away from the surface of the cured object in the direction from the surface of the cured object toward the inside. The film thickness of the planarization layer and the pixel division layer of the organic EL display device is usually in the range of 1000 to 5000nm. The place 500nm away from the surface of the cured object actually refers to the analysis of the central area inside the cured object. In the case where the planarization layer and / or the pixel division layer of the organic EL display element contains a cured object, it is preferred to perform TOF-SIMS analysis on the surface portion of the cured object in the area that is more than 2μm away from the end of the contact hole or the end of the pixel opening in the planar direction. The film thickness of the area less than 2μm away from the end of the contact hole or the end of the pixel opening in the planar direction may be less than 500nm. In this case, the mass spectrum information of the lower layer components outside the interior of the cured object may be mixed.

[0046] The information on the direction from the surface of the solidified object toward the inside obtained by TOF-SIMS analysis is usually obtained by converting the sputtering time into the distance from the surface of the object to the inside. Methods for converting the sputtering time into the distance from the surface of the object to the inside include, for example: a method of converting time into distance based on the relationship between the film thickness of the solidified object and the sputtering time from the surface of the solidified object to the inside of the solidified object, or a method of interrupting the acquisition of the distribution diagram in the TOF-SIMS analysis of the solidified object, measuring the distance from the surface of the obtained analysis pit to the inside with a stylus film thickness meter, and calculating the sputtering rate of the solidified object in advance, etc. The method for measuring the film thickness of the solidified object is not particularly limited. For example, the film thickness can be measured by electron microscopic observation of a cross section of the resin solidified object.

[0047] In the case of uneven composition, such as when the film components are distributed in the depth direction of the film, the sputtering rate, that is, the thickness of the sputtered film per unit time, is not exactly constant. However, in the present invention, there is no need to accurately define the area 500 nm from the surface of the solidified material, so the above-mentioned method of calculation does not pose a problem.

[0048] It should be noted that, for example, when analyzing a cured product included in an organic EL display device using the aforementioned TOF-SIMS, it is necessary to expose the surface of the cured product. An example of a method for exposing the surface of the cured product is described below, but the exposure method is not limited to the following method.

[0049] As a method for exposing the surface of the cured product, for example, a sputtering gun using argon, cesium, oxygen, gallium, or the like can be used to remove the upper surface of the target cured product, thereby exposing the surface of the cured product.

[0050] Alternatively, as an exposure method using chemical etching, one or both of the electrodes sandwiched above and below the pixel dividing layer can be dissolved with acid or alkali to create gaps above and below the cured product, and the laminate can be peeled off to expose the cured product surface.

[0051] In addition, as an exposure method using the oblique cutting method, the glass cover of the organic EL display device can be removed, and the stacked body including the exposed organic EL layer, pixel division layer, etc. can be collected and cut obliquely relative to the light extraction direction to expose the surface of the cured product.

[0052] Next, a cured product of the photosensitive resin composition containing (A) the alkali-soluble resin and (B) the naphthoquinonediazidesulfonic acid ester compound will be described.

[0053] The photosensitive resin composition contains (A) an alkali-soluble resin. Alkali-soluble means that a solution of the resin dissolved in γ-butyrolactone is applied to a silicon wafer, prebaked at 120°C for 4 minutes to form a prebaked film having a thickness of 10 μm ± 0.5 μm. The prebaked film is then immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23 ± 1°C for 1 minute, followed by rinsing with pure water. The dissolution rate, as determined by the reduction in film thickness, is 50 nm / minute or greater.

[0054] As (A) alkali-soluble resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyaminoamide, acrylic resin, Cardo resin, phenolic resin, cyclic olefin polymer, silicone resin etc. can be enumerated, but is not limited to this.Can contain these resins more than 2 kinds.In these alkali-soluble resins, preferably the resin with excellent heat resistance, few outgassing amount under high temperature.Specifically, it is preferred that the alkali-soluble resin of more than one in the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, their copolymer and polysiloxane is selected from.In addition, from the aspect of the excellent film physical properties such as bending resistance, it is further preferred that the alkali-soluble resin of more than one in the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and their copolymer is selected from.

[0055] With regard to the alkali-soluble resin of more than one in the group being composed of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and their copolymer that can be used as (A) alkali-soluble resin, in order to give above-mentioned alkali solubility, preferably in the structural unit of resin and / or its main chain end, there is an acidic group.As acidic group, for example, carboxyl, phenolic hydroxyl, sulfonic group etc. can be enumerated, among these, from the aspect that does not contain sulfur atom, preferably carboxyl or phenolic hydroxyl.In addition, preferably there is fluorine atom, when utilizing alkaline aqueous solution to develop, can give hydrophobicity to the interface of film and base material, suppress alkaline aqueous solution to infiltrate into interface.From the viewpoint of the effect that prevents alkaline aqueous solution from infiltrating into interface, the fluorine atom content in alkali-soluble resin is preferably more than 5 mass %, from the aspect of solubility in alkaline aqueous solution, preferably below 20 mass %.

[0056] (A) The alkali-soluble resin is synthesized using a known method. In the case of polyamic acid or polyamic acid ester, as a production method, for example, the following methods can be used for synthesis: a method of reacting tetracarboxylic dianhydride with a diamine compound at low temperature; a method of reacting tetracarboxylic dianhydride with a diamine compound at low temperature, and then partially esterifying the amic acid structure using N,N-dimethylformamide dimethyl acetal or the like; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the diester with an amine in the presence of a condensing agent; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the remaining diformyl dichloride with an amine; and the like.

[0057] In the case of polyimide, for example, it can be obtained by dehydrating and ring-closing the polyamic acid or polyamic acid ester obtained by the above-mentioned method by heating or chemical treatment with an acid, an alkali, or the like in a solvent.

[0058] In the case of polybenzoxazole precursors, they can be produced by condensing a bisaminophenol compound with a dicarboxylic acid. Specifically, these methods include reacting a dehydrating condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding the bisaminophenol compound to the reaction; and adding a solution of dicarboxylic acid dichloride dropwise to a solution of the bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0059] In the case of polybenzoxazole, for example, it can be obtained by dehydrating and ring-closing the polybenzoxazole precursor obtained by the above-mentioned method by heating or chemical treatment with acid, alkali, etc. in a solvent.

[0060] Specific examples of acid dianhydrides that can be used as polyimides, polyimide precursors, and copolymers thereof include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic 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, and 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride. Aliphatic tetracarboxylic dianhydrides such as bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic dianhydride may be used. Two or more of these may be used.

[0061] Examples of dicarboxylic acids used as the acid component of polybenzoxazole, polybenzoxazole precursor, and copolymer thereof include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyldicarboxylic acid, and the like. Examples of tricarboxylic acids include trimellitic acid, pyromellitic acid, diphenyl ether trimethyl acid, and biphenyl trimethyl acid. Examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3 Aliphatic tetracarboxylic acids such as 1,1-bis(3,4-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-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, butanetetracarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid may be used. Two or more of these may be used.

[0062] Specific examples of diamines include 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-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, Benzene, 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, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or compounds obtained by replacing at least a portion of hydrogen atoms in their aromatic rings with alkyl groups and / or halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines of the structures shown below. Two or more of these may be used.

[0063] [Chemical Formula 1]

[0064]

[0065] R 1 、R 4 represents an oxygen atom, C(CF3)2, or C(CH3)2. 2 、R 3 、R 5 ~R 12 Each independently represents a hydrogen atom or a hydroxyl group.

[0066] These diamines can be used in the form of diamines, or in the form of corresponding diisocyanate compounds or trimethylsilylated diamines.

[0067] Furthermore, by capping the ends of these resins with known monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids having an acidic group, a resin having an acidic group at the end of the main chain can be obtained.

[0068] The content of the terminal blocking agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid, etc. is preferably 2 to 25 mol % based on 100 mol % of the total of the acid and amine components constituting the resin.

[0069] As the acrylic resin, those obtained by radical polymerization of (meth)acrylic acid or (meth)acrylate are preferred. As the (meth)acrylate, known ones such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, adamantyl methyl (meth)acrylate, and 1-methyladamantyl (meth)acrylate can be used. Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene may be copolymerized with the above-mentioned (meth)acrylic acid and (meth)acrylate.

[0070] Alternatively, an ethylenically unsaturated double bond group can be introduced by subjecting an epoxy compound having an ethylenically unsaturated double bond group to an addition reaction with (meth)acrylic acid.

[0071] Cardo resins include resins having a cardo structure, that is, a skeleton structure in which two ring structures are bonded to a quaternary carbon atom constituting a ring structure. A typical cardo structure is a structure in which a benzene ring is bonded to a fluorene ring.

[0072] Specific examples of the skeleton structure in which two cyclic structures are bonded to the quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and a fluorene skeleton having an acryloyl group.

[0073] Cardo resins are formed by polymerizing a skeleton having a cardo structure through reactions between functional groups bonded thereto. Cardo resins have a structure (cardo structure) in which a main chain and bulky side chains are connected by a single element, and have a cyclic structure in a direction approximately perpendicular to the main chain.

[0074] Specific examples of monomers having a cardo structure include known substances such as bis(glycidyloxyphenyl)fluorene-type epoxy resins, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and other cardo structure-containing bisphenols, 9,9-bis(cyanomethyl)fluorene and other 9,9-bis(cyanoalkyl)fluorenes, and 9,9-bis(3-aminopropyl)fluorene and other 9,9-bis(aminoalkyl)fluorenes.

[0075] Cardo resin is a polymer obtained by polymerizing monomers having a cardo structure, and may be a copolymer with other copolymerizable monomers.

[0076] The phenolic resin includes known phenolic resins such as Novolac phenolic resin and Resol phenolic resin, which can be obtained by polycondensing a mixture of one or more phenols among various phenols with an aldehyde such as formaldehyde.

[0077] Examples of the phenols constituting the Novolac phenolic resin and the Resol phenolic resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol (methylephenol), and bisphenol A. The present invention also includes but is not limited to phenol, anthracene, phenol, bis-p-cresol, methylenebis-p-cresol, resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc., which can be used alone or in a mixture of multiple types.

[0078] In addition, examples of aldehydes include, in addition to formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, and these may be used alone or in combination of two or more.

[0079] The preferred weight average molecular weight of the phenolic resin used in the present invention, as measured by gel permeation chromatography in terms of polystyrene, is preferably 2,000 to 50,000, and more preferably 3,000 to 30,000. A weight average molecular weight exceeding 50,000 tends to deteriorate developability and sensitivity, while a weight average molecular weight below 2,000 tends to deteriorate pattern shape, resolution, developability, and heat resistance.

[0080] Examples of the polysiloxane include known polysiloxanes obtained by hydrolyzing one or more selected from tetrafunctional organosilanes, trifunctional organosilanes, bifunctional organosilanes, and monofunctional organosilanes, followed by dehydration condensation.

[0081] Specific examples of organosilanes include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane and other tetrafunctional silanes; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, para-hydroxy Phenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl) Trifunctional silanes such as ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, and 2-naphthyltrimethoxysilane; dimethyldimethoxysilane, dimethyl Bifunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, and di(1-naphthyl)diethoxysilane; and monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane. Two or more of these organosilanes may be used. Furthermore, silicate compounds such as methyl silicate 51 manufactured by Fuso Chemical Co., Ltd. and M silicate 51 manufactured by Tama Chemical Co., Ltd. may be copolymerized.

[0082] The weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but a weight average molecular weight (Mw) of 1,000 or more in terms of polystyrene as measured by GPC (gel permeation chromatography) is preferred because coating properties are improved. On the other hand, from the perspective of solubility in a developer, it is preferably 100,000 or less, and more preferably 50,000 or less.

[0083] Polysiloxanes are synthesized by hydrolyzing monomers such as organosilanes and partially condensing them. Partial condensation, as used herein, means that some Si-OH groups remain in the resulting polysiloxane, not that all Si-OH groups in the hydrolyzate are condensed. Conventional methods can be used for hydrolysis and partial condensation. For example, a method can be used in which a solvent and water are added to an organosilane mixture, along with a catalyst as needed, and then heated and stirred at 50-150°C for approximately 0.5-100 hours. During stirring, hydrolysis byproducts (alcohols such as methanol) and condensation byproducts (water) can be removed by distillation as needed.

[0084] There are no particular restrictions on the catalyst, but acid catalysts and base catalysts are preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, and ion exchange resins. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having an amino group, and ion exchange resins.

[0085] The photosensitive resin composition contains (B) a naphthoquinonediazidesulfonic acid ester compound. The naphthoquinonediazidesulfonic acid ester compound is preferably a compound in which the sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group in the form of an ester.

[0086] The compounds having a phenolic hydroxyl group used herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, MethyleneTris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, and TML-HQ. 、TML-pp-BPF、TML-BPA、TMOM-BP、HML-TPPHBA、HML-TPHAP(trade name, made by Honshu Chemical Industry Co., Ltd.), BIR-OC、BIP-PC、BIR-PC、BIR-PTBP、BIR-PCHP、BIP-BIOC-F、4PC、BIR-BIPC-F、TEP-BIP-A、46DMOC、46DMOEP、TM-BIP-A(trade name, made by Asahi Organic Materials Industry Co., Ltd. Preferred examples include compounds obtained by introducing naphthoquinonediazide-4-sulfonic acid or naphthoquinonediazide-5-sulfonic acid into compounds such as bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) in the form of an ester bond. Compounds other than these may also be used.

[0087] The naphthoquinone diazide sulfonic acid ester compounds can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized using known methods. The use of these naphthoquinone diazide sulfonic acid ester compounds can further improve resolution, sensitivity, and residual film rate.

[0088] Naphthoquinonediazide-4-sulfonate compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. Naphthoquinonediazide-5-sulfonate compounds have absorption extending into the g-line region of a mercury lamp and are suitable for g-line exposure. The present invention can use either naphthoquinonediazide-4-sulfonate compounds or naphthoquinonediazide-5-sulfonate compounds. Naphthoquinonediazide-4-sulfonate compounds containing both naphthoquinonediazide-5-sulfonyl groups in the same molecule can also be used. Furthermore, a mixture of naphthoquinonediazide-4-sulfonate compounds and naphthoquinonediazide-5-sulfonate compounds can be used.

[0089] Among these, naphthoquinonediazidesulfonate compounds decompose during the heat treatment process, with a portion being removed from the film as sulfur dioxide. Therefore, naphthoquinonediazide-4-sulfonate compounds are preferred from the perspective of reducing the amount of sulfur atoms contained in the cured product. Furthermore, by using a naphthoquinonediazide-4-sulfonate compound in conjunction with the base generator (C) described below, the decomposition of the naphthoquinonediazidesulfonate compound and the removal of sulfur dioxide from the film during the heat treatment process can be significantly accelerated, further reducing the amount of sulfur atoms contained in the cured product. This further suppresses pixel shrinkage caused by sulfur atoms, making it particularly preferred.

[0090] The content of the naphthoquinonediazide-4-sulfonate compound (B1) is preferably in the range of 60% to 100% by mass relative to the total amount (100% by mass) of the naphthoquinonediazidesulfonate compound (B). A content of 60% by mass or greater can effectively reduce the amount of sulfur atoms contained in the cured product. A content of 70% by mass or greater is more preferred, and 80% by mass or greater is even more preferred.

[0091] The amount of the naphthoquinone diazide sulfonic acid ester compound (B) added is preferably 4% by mass or greater, more preferably 5% by mass or greater, and even more preferably 6% by mass or greater, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total amount of the resin composition excluding the solvent. A content of 4% by mass or greater enables pattern formation with excellent sensitivity, while a content of 20% by mass or less suppresses pixel shrinkage caused by the sulfur atoms in the naphthoquinone diazide sulfonic acid ester compound, thereby improving the long-term reliability of the organic EL device.

[0092] The photosensitive resin composition preferably contains (C) an alkali generator. (C) The alkali generator refers to a compound that generates a base such as an amine upon heating. To prevent base generation during the heat drying step of the photosensitive resin composition, the base generation temperature is preferably 100°C or higher, more preferably 120°C or higher, and even more preferably 140°C or higher. To ensure sufficient base generation during the heat treatment step after development, the base generator is preferably 240°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower. The (C) alkali generator is preferably a compound that undergoes minimal photodecomposition at the exposure wavelength. In the present invention, the exposure wavelength preferably includes any of the i-line (365nm), h-line (405nm), and g-line (436nm) of a mercury lamp, and is preferably a compound that does not substantially photodecompose upon irradiation with these wavelengths. This suppresses base generation by the thermal alkali generator during the exposure process, thereby suppressing the deactivation of the acid generated by the (B) naphthoquinone diazidesulfonic acid ester compound due to exposure.

[0093] By generating a base from the above-mentioned (C) alkali generator in the heat treatment process, the decomposition of the (B) naphthoquinonediazidesulfonate compound and the removal of sulfur dioxide to the outside of the film are promoted. The effect of removing sulfur dioxide to the outside of the film is particularly significant when a naphthoquinonediazide-4-sulfonate compound is used as the (B) component. It is speculated that the reason is that the carbon-sulfur bond energy of the naphthoquinonediazide-4-sulfonate compound is smaller than the carbon-sulfur bond energy of the naphthoquinonediazide-5-sulfonate compound. Therefore, the severance of the carbon-sulfur bond caused by the heat and alkali in the heat treatment is particularly easy to occur in the naphthoquinonediazide-4-sulfonate compound. In the heat treatment process, the removal of sulfur oxides to the outside of the film is promoted, and as a result, the pixel shrinkage caused by the sulfur atoms can be further suppressed.

[0094] Examples of the base generated by the base generator (C) include primary amines, secondary amines, tertiary amines, quaternary ammoniums, imidazoles, pyrazoles, guanidines, biguanides, etc. Among these, the base generator (C) is preferably a guanidine derivative and / or a biguanide derivative because the base generated by the base generator (C) has high basicity.

[0095] Specific examples of the (C) alkali generating agent include U-CAT (registered trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851, U-CAT SA506, and U-CAT 5002 (trade names, manufactured by San-Apro Ltd.), WPBG-165, WPBG-027, WPBG-082, WPBG-266, WPBG-300, and WPBG-345 (trade names, manufactured by FUJIFILM WakoPure Chemical Co., Ltd.). Corporation), 2-(9-oxoxanthen-2-yl)propanoic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 2-(9-oxoxanthen-2-yl)propanoic acid 1,5-diazabicyclo[4.3.0]non-5-ene, 2-(9-oxoxanthen-2-yl)propanoic acid 1,8-diazabicyclo[5.4.0]undec-7-ene, [[(2-nitrobenzyl)oxy]carbonyl ] cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexamethylenediamine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]hexamethylenediamine, N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,6-dimethylpiperidine, N-tert-butoxycarbonyl-4-piperidinyl acetic acid, N-tert-butoxycarbonyl Oxycarbonyl-piperidinyl-4-carboxylic acid, N-tert-butoxycarbonyl-4-aminobenzoic acid, 4-(tert-butoxycarbonyl-amino)cyclohexanone, 4-(tert-butoxycarbonyl-amino)phenol, N-tert-butoxycarbonyl-tyramine, N-tert-butoxycarbonyldimethylpiperidine, N-(tert-butoxycarbonyl)-prolinol, 1,3-bis(4-tert-butoxycarbonyl-aminophenoxy)benzene, 4,4'-bis(tert-butoxycarbonyl-amino)diphenyl methyl ether, 3,4'-bis(tert-butoxycarbonyl-amino)diphenyl ether, N-phenyliminodiacetic acid, 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid, N-methyliminodiacetic acid, N-benzyliminodiacetic acid, 2-(9-oxoxanthene-2-yl)propanoic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene, guanidinium 2-(3-benzoylphenyl)propionate, etc. These base generators may be used alone or in combination of two or more.

[0096] Among these base generating agents, examples of guanidine derivatives and / or biguanide derivatives include WPBG-266, WPBG-300, and WPBG-345 (these are trade names, manufactured by FUJIFILM Wako Pure Chemical Corporation), 1,5,7-triazabicyclo[4.4.0]dec-5-ene-2-(9-oxoxanthene-2-yl)propanoate, 1,5-diazabicyclo[4.3.0]non-5-ene-2-(9-oxoxanthene-2-yl)propanoate, and 1,8-diazabicyclo[5.4.0]undec-7-ene-2-(9-oxoxanthene-2-yl)propanoate.

[0097] The content of the base generator (C) is preferably 0.1% by mass or greater, more preferably 1% by mass or greater, and even more preferably 2% by mass or greater, relative to the total amount of the resin composition excluding the solvent. It is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. A content of 0.1% by mass or greater can suppress pixel shrinkage caused by the sulfur atom of the naphthoquinone diazide sulfonic acid ester compound, thereby improving the long-term reliability of the organic EL device. A content of 15% by mass or less can suppress adverse effects such as degradation of film properties.

[0098] The photosensitive resin composition preferably contains (D) an organic solvent, which can be used to form a varnish and improve coating properties.

[0099] The above organic solvents may be polar aprotic solvents such as γ-butyrolactone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, ketones such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, Esters such as diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, methyl acetoacetate, ethyl acetoacetate, and other esters, aromatic hydrocarbons such as toluene and xylene, and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0100] The amount of the organic solvent used is not particularly limited, but is preferably 100 to 3000 mass%, more preferably 150 to 2000 mass%, relative to the total amount of the resin composition excluding the solvent. Furthermore, the proportion of the solvent having a boiling point of 180°C or higher in the total amount of the organic solvent is preferably 20 mass% or less, more preferably 10 mass% or less. By limiting the proportion of the solvent having a boiling point of 180°C or higher to 20 mass% or less, the amount of outgassing from the planarization layer or the insulating layer after thermal curing can be suppressed to a low level, thereby improving the long-term reliability of the organic EL device.

[0101] The photosensitive resin composition may contain 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 oxetanyl groups, within its molecule. A thermal crosslinking agent can crosslink the resin (A) or other added components, improving the heat resistance, chemical resistance, and hardness of the thermally cured film. Furthermore, it can reduce outgassing from the cured product, thereby improving the long-term reliability of the organic EL display device. Therefore, its inclusion is preferred.

[0102] Two or more thermal crosslinking agents may be used in combination.

[0103] The content of the thermal crosslinking agent is preferably from 1% to 30% by mass relative to the total amount of the resin composition excluding the solvent. When the content of the thermal crosslinking agent is from 1% to 30% by mass, the chemical resistance and hardness of the film after firing or curing can be improved, and the amount of outgassing from the cured product can be reduced, thereby improving the long-term reliability of the organic EL display device and providing excellent storage stability of the photosensitive resin composition.

[0104] The photosensitive resin composition used in the present invention may contain a colorant. The so-called colorant refers to an organic pigment, inorganic pigment, or dye commonly used in the field of electronic information materials. The colorant is preferably an organic pigment and / or an inorganic pigment.

[0105] Examples of the organic pigment include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo or polyazo, phthalocyanine pigments such as copper phthalocyanine, copper phthalocyanine halide or non-metallic phthalocyanine, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthraquinone, indanthrone, pyranthrone or anthrone violet, quinacridone pigments, bisoxizone pigments, pyrenone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, benzofuranone pigments or metal complex pigments.

[0106] Examples of the inorganic pigment include titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, white aluminum oxide, kaolin, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum red, molybdenum orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chrome green, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Prussian blue, cobalt blue, cerulean blue, cobalt silicon blue, cobalt zinc silicon blue, manganese violet, and cobalt violet.

[0107] Examples of the dye include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigo dyes, carbonium dyes, phthalocyanine dyes, methine or polymethine dyes.

[0108] For the purpose of improving the contrast of the organic EL display device, the color of the colorant is preferably black, which can block visible light in the entire wavelength range. At least one or more selected from organic pigments, inorganic pigments and dyes can be used, and a colorant that is black when formed into a cured film can be used. Therefore, the above-mentioned black organic pigments and black inorganic pigments can be used, and two or more organic pigments and dyes can be mixed to approximate black. When approximate black, it can be obtained by mixing two or more of the above-mentioned red, orange, yellow, purple, blue, green and other organic pigments and dyes. It should be noted that the photosensitive resin composition of the present invention itself does not necessarily have to be black, and a colorant that changes color during heat curing and makes the cured film black can be used.

[0109] Among these, colorants containing organic pigments and / or inorganic pigments and exhibiting a black color when formed into a cured film are preferred from the perspective of ensuring high heat resistance. Furthermore, colorants containing organic pigments and / or dyes and exhibiting a black color when formed into a cured film are preferred from the perspective of ensuring high insulation properties. Specifically, colorants containing organic pigments and exhibiting a black color when formed into a cured film are preferred from the perspective of achieving both high heat resistance and high insulation properties.

[0110] The content of the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total amount of the resin composition excluding the solvent, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. A colorant content of 5% by mass or more can achieve the desired colorability of the cured film, while a colorant content of 50% by mass or less can improve storage stability.

[0111] In the photosensitive resin composition of the present invention, when a pigment is used as a colorant, a dispersant is preferably used in combination. By using a dispersant in combination, the colorant can be uniformly and stably dispersed in the resin composition. The dispersant is not particularly limited, but is preferably a polymer dispersant. Examples of polymer dispersants include polyester polymer dispersants, acrylic polymer dispersants, polyurethane polymer dispersants, polyallylamine polymer dispersants, and carbodiimide polymer dispersants. More specifically, the so-called polymer dispersant refers to a polymer compound whose main chain is formed by polyamino, polyether, polyester, polyurethane, polyacrylate, etc., and has polar groups such as amine, carboxylic acid, phosphoric acid, amine salt, carboxylate, and phosphate at the side chain or the end of the main chain. The polar group is adsorbed on the pigment and plays a role in stabilizing the dispersion of the pigment through the steric hindrance of the main chain polymer.

[0112] Dispersants can be classified into (polymer) dispersants having only an amine value, (polymer) dispersants having only an acid value, (polymer) dispersants having both an amine value and an acid value, or (polymer) dispersants having neither an amine value nor an acid value. Preferred are (polymer) dispersants having both an amine value and an acid value, and (polymer) dispersants having only an amine value. More preferred are (polymer) dispersants having only an amine value.

[0113] In order to improve dispersion stability while maintaining heat resistance, the ratio of the dispersant to the colorant is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 100% by mass or less, more preferably 50% by mass or less.

[0114] The photosensitive resin composition used in the present invention may contain a close-fitting improver. Examples of the close-fitting improver include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and other silane coupling agents, titanium chelates, aluminum chelates, and compounds obtained by reacting an aromatic amine compound with an alkoxy-containing silicon compound. Two or more of these may also be contained. By containing these close-fitting improvers, when developing the photosensitive resin film, adhesion to substrates such as silicon wafers, ITO, SiO 2 , and silicon nitride can be improved. Furthermore, resistance to oxygen plasma and UV ozone treatments for cleaning can be improved. The content of the adhesion improver is preferably 0.1 to 10% by mass based on the total amount of the resin composition excluding the solvent.

[0115] For the purpose of improving wettability with the substrate, the photosensitive resin composition used in the present invention may contain a surfactant as needed. Surfactants can be commercially available compounds. Specifically, as silicone surfactants, there can be mentioned SH series, SD series, ST series of Dow Corning Toray Silicone Company, Ltd., BYK series of BYK JapanKK, KP series of Shin-Etsu Silicone, Disfoam series of NOF Corporation, TSF series of Toshiba Silicone Co., Ltd., etc. As fluorine-based surfactants, there can be mentioned "MEGAFAC (registered trademark)" series of Dainippon Ink & Chemicals, Inc., FLUORAD series of Sumitomo 3M Limited, "SURFLON (registered trademark)" series, "AsahiGuard (registered trademark)" series of Asahi Glass Co., Ltd., EF series of Shin-Akita Chemical Co., Ltd., OMNOVA Solutions Co., Ltd.'s PolyFox series, and surfactants composed of acrylic and / or methacrylic polymers include, but are not limited to, Kyoeisha Chemical Co., Ltd.'s POLYFLOW series and Kusumoto Chemical Co., Ltd.'s "DISPARLON (registered trademark)" series.

[0116] The content of the surfactant is preferably 0.001 to 1% by mass based on the total amount of the resin composition excluding the solvent.

[0117] The photosensitive resin composition used in the present invention may contain a compound having a phenolic hydroxyl group for the purpose of improving the alkali developability of the photosensitive resin composition as needed. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (TetrakisP-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, and BisPC-OCHP. , Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, MethyleneTris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, B IR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Industries, Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-hydroxyquinoline, etc. By containing these compounds having a phenolic hydroxyl group, the resulting photosensitive resin composition is almost insoluble in an alkaline developer before exposure, but readily dissolves in an alkaline developer during exposure. Therefore, film loss due to development is minimal, and development is facilitated in a short time. Consequently, sensitivity is readily improved.

[0118] The content of the compound having a phenolic hydroxyl group is preferably 1% by mass or more and 20% by mass or less based on the total amount of the resin composition excluding the solvent.

[0119] The photosensitive resin composition used in the present invention may also contain inorganic particles. Preferred examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, aluminum oxide, and talc. The primary particle size of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0120] The content of the inorganic particles is preferably 5 to 90% by mass based on the total amount of the resin composition excluding the solvent.

[0121] The photosensitive resin composition used in the present invention may contain a thermal acid generator within a range that does not impair the long-term reliability of the organic EL display device. The thermal acid generator generates acid upon heating, accelerating the crosslinking reaction of the thermal crosslinker. Furthermore, if the resin (component (A)) contains unclosed imide ring structures or oxazole ring structures, it can promote their cyclization, further improving the mechanical properties of the cured film.

[0122] The thermal decomposition starting temperature of the thermal acid generator used in the present invention is preferably 50°C to 270°C, more preferably 250°C or lower. Furthermore, it is preferred to select a thermal acid generator that does not generate acid during drying (pre-baking: approximately 70°C to 140°C) after the photosensitive resin composition of the present invention is applied to a substrate, but generates acid during final heating (curing: approximately 100°C to 400°C) after patterning by subsequent exposure and development. This can suppress a decrease in sensitivity during development, which is therefore preferred.

[0123] The acid generated by the thermal acid generator used in the present invention is preferably a strong acid, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid, and halogenated alkylsulfonic acids such as trifluoromethanesulfonic acid. These are used in the form of salts such as onium salts or in the form of covalently bonded compounds such as imidosulfonates. Two or more of these may be contained.

[0124] The content of the thermal acid generator used in the present invention is preferably 0.01% by mass or greater, more preferably 0.1% by mass or greater, relative to the total amount of the resin composition excluding the solvent. The inclusion of 0.01% by mass or greater promotes crosslinking reactions and cyclization of unclosed ring structures in the resin, thereby further improving the mechanical properties and chemical resistance of the cured film. Furthermore, from the perspective of long-term reliability of organic EL displays, the content is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.

[0125] The method for producing a cured product of a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinonediazidesulfonic acid ester compound of the present invention is a method for producing a cured product, comprising the following steps in sequence: a step of applying the photosensitive resin composition to a substrate to form a photosensitive resin film; a step of drying the photosensitive resin film; a step of exposing the dried photosensitive resin film; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film to obtain a cured product, wherein the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the cured product is set to 1 (S) (Unit: counts), the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) (Unit: counts), the intensity ratio I (S) / I (TOTAL) is 0.0001 or more and 0.008 or less. Furthermore, in the method for producing the cured product, the maximum heating temperature in the step of heat-treating the cured product is preferably 250°C or more and 400°C or less. Furthermore, it is preferred that the developed photosensitive resin film be irradiated with ultraviolet light between the step of developing the photosensitive resin film and the step of heat-treating the photosensitive resin film to obtain the cured product.

[0126] Next, the process of coating the photosensitive resin composition on a substrate to form a photosensitive resin film is described. The photosensitive resin composition of the present invention is coated on a substrate using a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc. to obtain a coating film of the photosensitive resin composition. The substrate to be coated with the photosensitive resin composition can be pretreated with the above-mentioned adhesion improver before coating. For example, the following method can be mentioned: using a solution obtained by dissolving 0.5 to 20 weight% of the adhesion improver in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc., to treat the surface of the substrate. As a method for treating the surface of the substrate, spin coating, slit die coating, rod coating, dip coating, spray coating, steam treatment, etc. can be mentioned.

[0127] The substrate can appropriately select metal, glass, resin film etc. for the support of display device, the preferred substrate for the transportation of subsequent process. When it is a glass substrate, soda-lime glass, alkali-free glass etc. can be used. In addition, the thickness is also as long as it is a thickness sufficient for maintaining mechanical strength. About the material of glass, the fewer the ions dissolved from the glass, the better, therefore alkali-free glass is preferred. Since soda-lime glass with barrier coatings such as SiO2 is implemented, it is also commercially available, so such soda-lime glass can be used. When it is a resin film, it is preferably included to be selected from polyimide, polyamide, polybenzoxazole, polyamide-imide and poly (para-xylene) resin material, these resin materials can be included alone, or a variety of combinations can be made. For example, in the case of being formed by polyimide resin, it is also possible to apply a solution of a polyamic acid (including a part of imidized polyamic acid) or a soluble polyimide as a precursor of polyimide to a supporting substrate, and sintering and forming.

[0128] Next, the step of drying the photosensitive resin film will be described.

[0129] After coating, the coating is dried under reduced pressure as needed, and then heat-treated at 50° C. to 180° C. for 1 minute to several hours using a hot plate, an oven, infrared rays, or the like to obtain a photosensitive resin film.

[0130] Next, the step of exposing the dried photosensitive resin film to light will be described.

[0131] The photosensitive resin film is irradiated with actinic rays through a mask having a desired pattern. Examples of actinic rays used for exposure include ultraviolet rays, visible light, electron beams, and X-rays. In the present invention, the i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp are preferably used.

[0132] Next, the step of developing the exposed photosensitive resin film will be described.

[0133] After exposure, the exposed portion is removed using a developer. As a developer, aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and 1,6-hexanediamine are preferred. Furthermore, 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 isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added to these alkaline aqueous solutions, either alone or in combination, depending on the circumstances. Development methods include spraying, puddle immersion, immersion, and ultrasonic waves.

[0134] Next, the pattern formed by the development is preferably rinsed with distilled water.

[0135] Here, the rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and the like to distilled water.

[0136] Next, the step of irradiating the developed photosensitive resin film with ultraviolet rays will be described.

[0137] By ultraviolet irradiation, the (B) naphthoquinonediazidesulfonic acid ester compound is converted into an indenecarboxylic acid compound. The indenecarboxylic acid compound further promotes the removal of sulfur dioxide from the sulfonic acid ester structure to the outside of the film in the heat treatment step described later. Therefore, the sulfur concentration in the cured product can be further reduced, and the long-term reliability of the organic EL device can be further improved. Here, the ultraviolet light is preferably light of any wavelength including the i-line (365nm), h-line (405nm), and g-line (436nm) of a mercury lamp, and the irradiation amount is preferably 100 to 10,000 mJ / cm 2 By treating with these wavelengths and irradiation doses, it is possible to efficiently convert into an indene carboxylic acid compound.

[0138] Next, a description will be given of a step of obtaining a cured product by heat-treating the developed photosensitive resin film.

[0139] By heat treatment, residual solvents and components with low heat resistance can be removed, thereby improving heat resistance and chemical resistance. In particular, when the (A) alkali-soluble resin contained in the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, or a copolymer thereof, heat treatment can form an imide ring or an oxazole ring, thereby improving heat resistance and chemical resistance. In addition, when a thermal crosslinking agent is included, heat treatment can cause the thermal crosslinking reaction to proceed, thereby improving heat resistance and chemical resistance. In addition, when an alkali generator (C) is included, a base is generated by heat treatment, and sulfur dioxide from the sulfonate structure of the naphthoquinone diazide sulfonate compound (B) can be removed to the outside of the film.

[0140] The heat treatment can be maintained at the maximum heating temperature after stepwise temperature increase, can be maintained at the maximum heating temperature after continuous temperature increase, or can be maintained at the maximum heating temperature from the beginning. Here, the so-called maximum heating temperature refers to: for the temperature experienced by the resin film due to heating, the temperature range above which the resin film has experienced for a cumulative period of more than 1 minute is confirmed, wherein the highest temperature is the maximum heating temperature. From the perspective of fully carrying out the reaction of removing sulfur dioxide from the sulfonic acid ester structure of the naphthoquinonediazidesulfonic acid ester compound (B) to the outside of the film, the maximum heating temperature is preferably 240°C or more, more preferably 250°C or more, and further preferably 260°C or more. In addition, from the perspective of avoiding the influence of thermal degradation of the TFT element, it is preferably 420°C or less, more preferably 400°C or less, further preferably 350°C or less, and particularly preferably 320°C or less. The holding time at the maximum heating temperature is not particularly limited. However, from the perspective of sufficient reaction to remove sulfur dioxide derived from the sulfonate structure of the naphthoquinonediazidesulfonate compound (B) to the outside of the membrane, the holding time is preferably 15 minutes or longer, more preferably 30 minutes or longer, and even more preferably 45 minutes or longer. Furthermore, from the perspective of productivity, the holding time is preferably 180 minutes or shorter, more preferably 150 minutes or shorter, and even more preferably 120 minutes or shorter.

[0141] Next, a method for manufacturing an organic EL display device will be described.

[0142] In a method for manufacturing an organic EL display device comprising the steps of sequentially forming a planarization layer, a first electrode, a pixel division layer, an organic EL layer, and a second electrode on a substrate, the method for manufacturing a cured product contained in the planarization layer and / or the pixel division layer is a method for manufacturing a cured product comprising the following steps in sequence: applying a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinonediazidesulfonic acid ester compound to a substrate to form a photosensitive resin film; drying the photosensitive resin film; exposing the dried photosensitive resin film; developing the exposed photosensitive resin film; and heating the developed photosensitive resin film to obtain a cured product.

[0143] The negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the solidified material was set as I (S) (Unit: counts), the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) (Unit: counts), the intensity ratio I (S) / I (TOTAL) It is preferably 0.0001 or more and 0.008 or less.

[0144] In the method for producing the cured product, the maximum heating temperature in the step of performing heat treatment to obtain the cured product is preferably 250° C. or higher and 400° C. or lower.

[0145] In addition, it is preferred that a step of irradiating the photosensitive resin film with ultraviolet light be included between the step of developing the photosensitive resin film and the step of heat-treating the photosensitive resin film. The ultraviolet light preferably includes light of any wavelength among the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, and the irradiation dose is preferably 100 to 10,000 mJ / cm 2 By treating with these wavelengths and irradiation doses, it is possible to efficiently convert into an indene carboxylic acid compound.

[0146] Example

[0147] Hereinafter, the present invention will be described with reference to Examples, etc., but the present invention is not limited to these Examples. The photosensitive resin compositions and organic EL display devices in the Examples were evaluated by the following methods.

[0148] (1) Sensitivity evaluation

[0149] Calculation of Exposure Sensitivity

[0150] The photosensitive resin composition obtained by each embodiment and comparative example was coated on an 8-inch silicon wafer using a coating and developing device ACT-8 (manufactured by Tokyo Electron Co., Ltd.) by a spin coating method, and baked at 120°C for 3 minutes using a hot plate to prepare a pre-baked film with a film thickness of 3.0 μm. It should be noted that the film thickness was measured using LambdaAce STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under the condition of a refractive index of 1.63. Then, an i-line stepper exposure machine NSR-2005i9C (manufactured by Nikkon Corporation) was used to expose the film at a rate of 100 to 700 mJ / cm through a mask having a pattern of contact holes of 10 μm. 2 The exposure dose is 10mJ / cm 2 After exposure, the film was developed using the ACT-8 developing apparatus described above using a 2.38% by mass tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) for a time period until the film loss during development reached 0.5 μm. The film was then rinsed with distilled water and dried to obtain a pattern.

[0151] The pattern of the developed film was observed at 20-fold magnification using an FDP microscope MX61 (manufactured by Olympus Corporation), and the minimum exposure required to achieve a contact hole opening diameter of 10 μm was determined as exposure sensitivity.

[0152] (2) TOF-SIMS analysis of solidified materials

[0153] <Production of Cured Products>

[0154] Figure 2A schematic diagram of the substrate used is shown below. First, a 100 nm thick ITO transparent conductive film is formed on the entire surface of a 38×46 mm alkali-free glass substrate 11 by sputtering, and then etched to form a first electrode 12. In addition, an auxiliary electrode 13 for extracting the second electrode is also formed at the same time. The obtained substrate is ultrasonically cleaned for 10 minutes using "Semico Clean 56" (trade name, manufactured by Furuuchi Chemical Corporation), and then cleaned with ultrapure water. Next, a photosensitive resin composition (varnish) prepared according to the various embodiments and comparative examples described below is applied to the entire surface of the substrate by spin coating, and pre-baked on a hot plate at 120°C for 2 minutes. For this film, a parallel photomask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) is used, and an ultrahigh pressure mercury lamp is used as the light source (a mixed line of g-line, h-line, and i-line). After UV exposure through a photomask, it is developed using a 2.38% TMAH aqueous solution to dissolve only the exposed part, and then rinsed with pure water. Regarding the examples and comparative examples described as "bleaching after development" in Tables 1 to 4, PLA-501F was used at 500 mJ / cm 2 The entire surface is exposed with an exposure amount of . Using an inert oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.), the obtained patterned substrate is cured for 60 minutes in an oven under a nitrogen atmosphere at the temperature described in each embodiment and comparative example. In this way, openings with a width of 50 μm and a length of 260 μm are arranged at a spacing of 155 μm in the width direction and at a spacing of 465 μm in the length direction, and a pixel segmentation layer 14 is formed in a manner limited to the effective area of ​​the substrate, the pixel segmentation layer 14 having a shape in which the first electrode is exposed from each opening. In this way, a pixel segmentation layer with an aperture ratio of 18% is provided in the effective area of ​​the substrate which is a quadrilateral with a side length of 16 mm, and the thickness of the pixel segmentation layer is about 2.0 μm.

[0155] <Negative secondary ion detection based on TOF-SIMS depth analysis>

[0156] The cured product portion of the obtained substrate with the pixel partitioning layer was subjected to TOF-SIMS depth analysis using the following apparatus, and secondary ions generated during the TOF-SIMS depth analysis were measured.

[0157] Device: TOF.SIMS5 (manufactured by ION-TOF)

[0158] Etching ion type: Cs +

[0159] Etching ion acceleration energy: 2keV

[0160] Primary ion type: BI +

[0161] 1st ion energy: 25keV

[0162] Current value of primary ion: 0.4pA

[0163] Secondary ion polarity: Negative

[0164] Measurement area: 10 μm square

[0165] Measurement mode: High mass resolution

[0166] Anti-static: Irradiation of electron beam from immersion gun (electron gun)

[0167] Mass number of carbon negative secondary ion: 12

[0168] Mass number of oxygen negative secondary ion: 16

[0169] Mass number of fluorine negative secondary ion: 19

[0170] Mass number of silicon negative secondary ion: 28

[0171] Mass number of sulfur negative secondary ion: 32

[0172] In the mass spectrum information obtained by TOF-SIMS analysis of a location 500 nm from the film surface in the film depth direction of the cured product, the negative secondary ion intensity of sulfur was set as I. (S) (Unit: counts), the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) (Unit: counts) The distance 500 nm from the film surface was determined by converting the time into distance based on the relationship between the previously measured thickness of the cured film and the sputtering time from the surface of the cured product to the bottom surface of the cured product.

[0173] (3) Long-term reliability test of organic EL display devices

[0174] Production of Organic EL Display Devices

[0175] The same method as (2) was used to produce an organic EL display device using a substrate having a first electrode, an auxiliary electrode, and a pixel segmentation layer formed thereon. A nitrogen plasma treatment was performed as a pre-treatment, and then the organic EL layer 15 was formed by vacuum evaporation. It should be noted that the vacuum degree during evaporation was 1×10 -3Pa or less, and the substrate is rotated relative to the deposition source during the deposition. First, 10 nm of compound (HT-1) is deposited as a hole injection layer, and 50 nm of compound (HT-2) is deposited as a hole transport layer. Next, compound (GH-1) as the main material and compound (GD-1) as the doping material are deposited on the light-emitting layer with a thickness of 40 nm in such a way that the doping concentration becomes 10% by volume. Then, compound (ET-1) and (LiQ) as electron transport materials are stacked in a volume ratio of 1:1 to a thickness of 40 nm. The structures of the compounds used in the organic EL layer are shown below.

[0176] [Chemical Formula 2]

[0177]

[0178] Next, a 2nm thick compound (LiQ) was vapor-deposited, followed by 60nm of Mg and Ag at a volume ratio of 10:1 to form the second electrode 16. Finally, a cover glass plate was bonded using an epoxy resin adhesive in a low-humidity nitrogen atmosphere for sealing. Four square light-emitting devices, each 5mm in length, were fabricated on a single substrate. The film thickness indicated here is the value displayed by a quartz crystal oscillator-type film thickness monitor.

[0179] <Evaluation of long-term reliability>

[0180] The prepared organic EL display device was placed in a xenon tester (Q-SUN manufactured by Q-Lab Corporation) at an illumination of 800 W / m 2 The UV irradiation treatment was carried out under the conditions of 50°C. The organic EL display device was taken out every 50 hours and the UV irradiation was carried out at 10 mA / cm 2 The pixels were driven by direct current to emit light, and the luminescent area was measured. The minimum time required for the luminescent area to fall below 50° after UV irradiation, assuming the initial luminescent area before the UV irradiation test was 100°, was defined as the reliability of the organic EL display device (unit: hours). The device was evaluated according to the following criteria, with a reliability of 300 hours or more considered acceptable.

[0181] A+: Reliability over 650 hours

[0182] A: Reliability 600hr

[0183] A-: Reliability 550hr

[0184] B+: Reliability 500hr

[0185] B: Reliability 450hr

[0186] B-: Reliability 400hr

[0187] C: Reliability 350hr

[0188] D: Reliability 300hr

[0189] E: Reliability 200~250hr

[0190] F: Reliability 100~150hr

[0191] G: Unable to comment.

[0192] Synthesis Example 1 Synthesis of hydroxyl-containing diamine compounds

[0193] 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide and cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After the addition was complete, the mixture was reacted at -15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and vacuum-dried at 50°C.

[0194] 30g of the solid was placed in a 300mL stainless steel autoclave, dispersed in 250mL of methyl cellosolve, and 2g of 5% palladium-carbon was added. Hydrogen was introduced via a balloon, and a reduction reaction was carried out at room temperature. After approximately 2 hours, the balloon was confirmed to no longer deflate, and the reaction was terminated. After completion of the reaction, the catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to yield the hydroxyl-containing diamine compound represented by the following formula.

[0195] [Chemical Formula 3]

[0196]

[0197] Synthesis Example 2 Synthesis of polyimide precursor (A-1)

[0198] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of NMP. To this, 45.35 g (0.075 mol) of the hydroxyl-containing diamine compound obtained in Synthesis Example 1, 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the mixture was reacted at 20°C for 1 hour, followed by 2 hours at 50°C. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, a solution prepared by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble resin polyimide precursor (A-1).

[0199] Synthesis Example 3 Synthesis of polyimide (A-2)

[0200] Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 3.27 g (0.03 mol) of 3-aminophenol as a capping agent were dissolved in 150 g of N-methyl-2-pyrrolidone (NMP). 31.0 g (0.1 mol) of ODPA and 50 g of NMP were added thereto, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. 15 g of xylene was then added, and water and xylene were azeotroped together while stirring at 150°C for 5 hours. After stirring, the solution was poured into 3 L of water and a white precipitate was collected. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide (A-2) as an alkali-soluble resin.

[0201] Synthesis Example 4 Synthesis of polybenzoxazole precursor (A-3)

[0202] Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the solution was cooled to -15°C. A solution of 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Noyaku Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 25 g of γ-butyrolactone (GBL) was added dropwise so that the internal temperature did not exceed 0°C. After the addition, stirring was continued at -15°C for 6 hours. After the reaction was completed, the solution was poured into 3 L of water containing 10% by mass methanol, and a white precipitate was collected. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble resin, a polybenzoxazole (PBO) precursor (A-3).

[0203] Synthesis Example 5 Synthesis of polysiloxane (A-4)

[0204] A 500 ml three-necked flask was charged with 44.86 g (0.200 mol) of p-styryltrimethoxysilane (St), 39.66 g (0.200 mol) of phenyltrimethoxysilane (Ph), 6.81 g (0.050 mol) of methyltrimethoxysilane (Me), 13.12 g (0.050 mol) of 3-trimethoxysilylpropylsuccinic anhydride (Suc), 0.522 g of TBC, and 74.58 g of PGME. While stirring at room temperature, an aqueous solution of phosphoric acid (0.448 g of phosphoric acid dissolved in 27.90 g of water (0.50 mass % relative to the charged monomers)) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70°C and stirred for 90 minutes. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the three-necked flask (solution temperature) reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature was 100-110°C) to obtain a polysiloxane solution. It should be noted that the nitrogen flow rate was 0.05 liters / minute during the heating and heating and stirring. During the reaction, a total of 58.90 g of methanol and water were distilled as by-products. PGME was added to the obtained polysiloxane solution to a solids concentration of 40% by mass to obtain a polysiloxane (A-4) solution.

[0205] Synthesis Example 6 Synthesis of acrylic resin (A-5)

[0206] In a 500 ml flask, 5 g of 2,2'-azobis(isobutyronitrile), 5 g of tert-dodecyl mercaptan, and 150 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were added. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.0 2,6] 35 g of decane-8-yl ester was added, stirred at room temperature for a while, and after nitrogen substitution in the flask, heated and stirred at 70°C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the resulting solution, and heated and stirred at 90°C for 4 hours to obtain an acrylic resin solution. PGMEA was added to the resulting acrylic resin solution so that the solid content concentration became 40% by mass, to obtain an acrylic resin (A-5) solution.

[0207] Synthesis Example 7 Synthesis of naphthoquinone diazide-4-sulfonic acid ester compound (B-1)

[0208] Under a dry nitrogen flow, 21.22 g (0.05 mole) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mole) of naphthoquinone diazide-4-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the mixture was brought to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the temperature in the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain a naphthoquinone diazide-4-sulfonic acid ester compound (B-1) represented by the following formula.

[0209] [Chemical Formula 4]

[0210]

[0211] Synthesis Example 8 Synthesis of naphthoquinone diazide-5-sulfonic acid ester compound (B-2)

[0212] Under a dry nitrogen flow, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of naphthoquinonediazide-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the mixture was brought to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the temperature in the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitated precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain a quinonediazide compound (B-2) represented by the following formula.

[0213] [Chemical Formula 5]

[0214]

[0215] The alkali generating agents used in Examples and Comparative Examples are shown below.

[0216] C-1: WPBG-266 (manufactured by FUJIFILM Wako Pure Chemical Corporation), a compound having the following structure having a biguanide structure in its molecule

[0217] [Chemical Formula 6]

[0218]

[0219] C-2: WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation), a compound having the following structure having a biguanide structure in its molecule

[0220] [Chemical Formula 7]

[0221]

[0222] C-3: 4-(tert-butoxycarbonyl-amino)phenol

[0223] [Chemical Formula 8]

[0224]

[0225] C-4: N-tert-butoxycarbonyl-2,6-dimethylpiperidine

[0226] [Chemical Formula 9]

[0227]

[0228] C-5: N-(tert-butoxycarbonyl)-prolinol

[0229] [Chemical Formula 10]

[0230]

[0231] C-6: 1,3-bis(4-tert-butoxycarbonyl-aminophenoxy)benzene

[0232] [Chemical Formula 11]

[0233]

[0234] C-7: N-phenyliminodiacetic acid

[0235] [Chemical Formula 12]

[0236]

[0237] C-8: [[(2-Nitrobenzyl)oxy]carbonyl]cyclohexylamine

[0238] [Chemical Formula 13]

[0239]

[0240] C-9: WPBG082 (manufactured by FUJIFILM Wako Pure Chemical Corporation), a compound having the following structure

[0241] [Chemical Formula 14]

[0242]

[0243] Example 1

[0244] 10.0 g of the polyimide precursor (A-1), 1.0 g of (B-1), and 0.5 g of (C-1) obtained in Synthesis Example 2 were dissolved in 40.0 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) and 10.0 g of γ-butyrolactone (hereinafter referred to as GBL), and then filtered using a 0.2 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) to obtain a photosensitive resin composition A.

[0245] The obtained photosensitive resin composition A was used to determine the exposure sensitivity by the method described in the above <Calculation of Exposure Sensitivity>. Furthermore, a cured product was prepared by the method described in the above <Preparation of Cured Product>, and the negative secondary ion intensity I of sulfur was determined for the obtained cured product by the method described in the above <Negative Secondary Ion Detection by TOF-SIMS Depth Direction Analysis>. (S) , and the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon and sulfur I (TOTAL) , calculate I (S) / I (TOTAL) Furthermore, an organic EL display device was produced using the method described in the above-mentioned "Production of an Organic EL Display Device." The reliability of the resulting organic EL display device was evaluated using the method described in the above-mentioned "Evaluation of Long-term Reliability." The evaluation results are shown in Table 1.

[0246] Examples 2 to 25, Comparative Examples 1 to 21

[0247] Varnishes B to Y and varnishes a to u were obtained by the same method as in Example 1, using the types and amounts of the compounds as shown in Tables 1 to 5. In addition, the exposure sensitivity, I (S) / I (TOTAL) , Reliability of the Organic EL Display Device. The evaluation results are shown in Tables 1 to 5.

[0248] Results of long-term reliability tests on organic EL display devices

[0249] Compared with Comparative Examples 1 to 21 which do not satisfy the following conditions, Examples 1 to 25 which satisfy the following conditions have extremely good results in long-term reliability. The conditions are: an organic EL display device comprising a cured product of the photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a naphthoquinone diazide sulfonate compound, and the organic EL display device satisfies the condition that the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the cured product is set to I (S) (Unit: counts), the sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I (TOTAL) (Unit: counts), the intensity ratio I (S) / I (TOTAL) It should be noted that in Comparative Example 3, not only the exposed areas but also the non-exposed areas dissolved during development, and the desired pattern could not be obtained. Therefore, TOF-SIMS depth analysis and long-term reliability testing could not be performed.

[0250]

[0251]

[0252] [Table 3]

[0253]

[0254] [Table 4]

[0255]

[0256]

[0257]

[0258] Description of Reference Numerals

[0259] 1: Substrate

[0260] 2: TFT

[0261] 3: TFT insulation layer

[0262] 4: Wiring

[0263] 5: Flattening layer

[0264] 6: Contact hole

[0265] 7: First electrode

[0266] 8: Pixel segmentation layer

[0267] 9: Organic EL layer

[0268] 10: Second electrode

[0269] 11: Glass substrate

[0270] 12: First electrode

[0271] 13: Auxiliary electrode

[0272] 14: Pixel segmentation layer

[0273] 15: Organic EL layer

[0274] 16: Second electrode

Claims

1. An organic EL display device comprising a cured product of a photosensitive resin composition comprising an alkali-soluble resin A and a naphthoquinone diazide sulfonic acid ester compound B, wherein: The alkali-soluble resin A contains one or more alkali-soluble resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, copolymers thereof, and polysiloxane. The negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the solidified material was set as I S The sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I TOTAL When the intensity ratio I S / I TOTAL is 0.0001 or more and 0.006 or less, the I S , I TOTAL The unit is counts.

2. The organic EL display device according to claim 1, wherein The organic EL display device includes at least a substrate, a first electrode, a second electrode, an organic EL layer, a planarization layer, and a pixel division layer, and the cured product is contained in the planarization layer and / or the pixel division layer.

3. The organic EL display device according to claim 1 or 2, wherein: The photosensitive resin composition further contains a base generator C.

4. The organic EL display device according to claim 1 or 2, wherein: The naphthoquinonediazidesulfonic acid ester compound B contains a naphthoquinonediazide-4-sulfonic acid ester compound B1.

5. The organic EL display device according to claim 4, wherein The content of the naphthoquinonediazide-4-sulfonate compound B1 is 60% by mass or more and 100% by mass or less relative to 100% by mass of the total amount of the naphthoquinonediazidesulfonate compound B.

6. The organic EL display device according to claim 3, wherein The base generating agent C contains a guanidine derivative and / or a biguanide derivative.

7. A method for producing a cured product, comprising producing a cured product of a photosensitive resin composition comprising an alkali-soluble resin A and a naphthoquinone diazide sulfonate compound B. The alkali-soluble resin A contains one or more alkali-soluble resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, copolymers thereof, and polysiloxane. The method for manufacturing the solidified material comprises: a step of applying the photosensitive resin composition to a substrate to form a photosensitive resin film; a step of drying the photosensitive resin film; and a step of exposing the dried photosensitive resin film to light; The process of developing the exposed photosensitive resin film; irradiating the developed photosensitive resin film with ultraviolet rays; and heating the developed photosensitive resin film to obtain a cured product, wherein the negative secondary ion intensity of sulfur obtained by time-of-flight secondary ion mass spectrometry of the cured product is set as I S The sum of the negative secondary ion intensities of carbon, oxygen, fluorine, silicon, and sulfur is set to I TOTAL When the intensity ratio I S / I TOTAL is 0.0001 or more and 0.006 or less, the I S , I TOTAL The unit is counts.

8. The method for producing a cured product according to claim 7, wherein: The maximum heating temperature in the step of performing the heat treatment to obtain a cured product is 240° C. or higher and 420° C. or lower.

9. A method for manufacturing an organic EL display device, comprising the steps of sequentially forming a planarization layer, a first electrode, a pixel segmentation layer, an organic EL layer, and a second electrode on a substrate, wherein: A method for producing a cured product included in the planarization layer and / or the pixel partitioning layer includes the step of forming the cured product using the production method according to claim 7 or 8.

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