Organic el display device

Abstract

The present application relates to an organic EL display device with high long-term reliability and high bending reliability. The organic EL display device of the present application is an organic EL display device provided with a substrate having a first electrode, a pixel partition layer, an organic EL layer, and a second electrode on a base material, wherein the average value of ion intensity (I 75 C4H 12 N + ) detected in a range of 20 nm or more to 100 nm or less from the surface of the pixel partition layer toward the base material direction is 10.2 x 10 ‑4 or more. TMA‑1 ) is 1.0 x 10 ‑4 or more.

Description

TECHNICAL FIELD

[0001] The present application relates to an organic EL display device. BACKGROUND

[0002] In display devices having a thin display such as a smartphone, a tablet, and a television, many products using an organic electroluminescence (hereinafter, "organic EL") display device have been developed.

[0003] Generally, an organic EL display device has a driving circuit, a planarization layer, a first electrode, a pixel partition layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first electrode and second electrode or by flowing a current. Among them, as a material for the planarization layer and the pixel partition layer, a photosensitive resin composition capable of being patterned by ultraviolet irradiation is generally used. Among them, in the case of a photosensitive resin composition using a polyimide-based or polybenzoxazole-based resin, since the resin has high heat resistance and generates few gas components from the cured product, a highly reliable organic EL display device can be obtained, and thus it is preferably used from this point of view (for example, see Patent Literature 1).

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent Application Laid-Open No. 2002-91343 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] On the other hand, the requirement for high reliability of organic EL display devices has been becoming more severe year by year, and for the material for the planarization layer and the material for the pixel partition layer, long-term reliability after a reliability test under accelerated conditions such as high temperature, high humidity, and light irradiation without occurrence of a decrease in luminance of light emission or pixel shrinkage is required. Here, the so-called pixel shrinkage refers to a phenomenon in which the luminance of light emission decreases from the end of the pixel or becomes not lit.

[0009] In addition, in recent years, development of a flexible organic EL display device formed on a resin film substrate is actively being carried out. The flexible organic EL display device has a portion that can be bent in structure and / or a portion that is fixed in a bent state, and in these bent portions, a bending stress is sometimes applied to or has been applied to the planarization layer and the pixel partition layer. In the flexible organic EL display device including such a bent portion, peeling of the substrate from the organic EL layer sometimes occurs due to a bending operation, and as a result, the bending reliability of the organic EL display device sometimes decreases. Here, the so-called bending reliability refers to a phenomenon in which the luminance of light emission decreases from the end of the pixel or becomes not lit due to the bending operation.

[0010] It is difficult to say that the materials proposed in the patent documents listed above have sufficient performance for the long-term reliability and bending reliability requirements in recent years. The present application, in view of the above problems, aims to provide an organic EL display device with high long-term reliability and bending reliability.

[0011] Means for solving the problems

[0012] To solve the above problems, the organic EL display device of the present application has the following configuration.

[0013] [1] An organic EL display device, which is an organic EL display device provided with a substrate having a first electrode, a pixel partition layer, an organic EL layer, and a second electrode on a base material, wherein the average value of ion intensity (Iavg) detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm or more and 100 nm or less from the surface of the pixel partition layer toward the base material direction is 75 C4H 12 N + 10.2 x 10 TMA-1 or more. -4 1.0 x 10 -4 or less.

[0014] [2] The organic EL display device according to [1], wherein the average value of ion intensity (Iavg) detected by time-of-flight secondary ion mass spectrometry in a range of 101 nm or more and 300 nm or less from the surface of the pixel partition layer toward the base material direction is 75 C4H 12 N + 5.0 x 10 TMA-2 or less. -4

[0015] [3] The organic EL display device according to [1] or [2], wherein the average value of ion intensity (Iavg) detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm or more and 300 nm or less from the surface of the pixel partition layer toward the base material direction is 31 CF + 0.5 x 10 CF or less. -4

[0016] [4] The organic EL display device according to any one of [1] to [3], wherein the pixel partition layer contains a polyimide and / or a polybenzoxazole, and the polyimide and / or the polybenzoxazole have a structure represented by formula (1).

[0017] [Chemical Formula 1]

[0018] ​​

[0019] (In formula (1), X 1 represents a noncyclic divalent hydrocarbon group having 4 to 10 carbon atoms, R 1 each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and a each independently represents an integer of 0 to 4.)

[0020] [5] The organic EL display device according to [4], wherein X 1 in the aforementioned formula (1) is a structure represented by formula (2).

[0021] [Chemical Formula 2]

[0022]

[0023] (In formula (2), R 2 and R 3 each independently represents a noncyclic hydrocarbon group having 1 to 9 carbon atoms or a hydrogen atom, represents a bonding site bonded to an aromatic ring. Note that the total number of carbon atoms of R 2 and R 3 is 3 to 9.)

[0024] [6] The organic EL display device according to any one of [1] to [5], wherein the aforementioned pixel division layer has a maximum in the range of 1365 cm -1 to 1385 cm -1 in an infrared spectroscopic spectrum measured by a Fourier transform infrared spectrophotometer (FT-IR), and an index A indicating the amount of existence of an imide structure contained in the pixel division layer is 0.10 or more and 1.10 or less.

[0025] Index A = (maximum value in the range of 1365 cm -1 to 1385 cm -1 ) / (maximum value in the range of 1590 cm -1 to 1610 cm -1 )

[0026] (wherein the maximum value used in the aforementioned index A is an intensity value of an absorption maximum measured by FT-IR.)

[0027] [7] The organic EL display device according to any one of [1] to [6], wherein the aforementioned pixel division layer has a maximum in the range of 1040 cm -1 to 1060 cm -1 in an infrared spectroscopic spectrum measured by FT-IR, and an index B indicating the amount of existence of a benzoxazole structure with respect to the amount of existence of an imide structure contained in the pixel division layer is 0.20 or more and 2.50 or less.

[0028] Index B = (1040cm) -1 Above 1060cm -1 (the maximum value below) / (1365cm) -1 Above 1385cm -1 (The following are the maximum values)

[0029] (Among them, the maximum value used in index B above is the intensity value at the absorption maximum measured using FT-IR.)

[0030] [8] An organic EL display device as described in any one of [1] to [7], wherein the aforementioned pixel segmentation layer further comprises a compound from a thermally generated acid agent.

[0031] [9] An organic EL display device as described in any one of [1] to [8], wherein the aforementioned pixel segmentation layer further comprises a compound from a resin containing phenolic hydroxyl groups.

[0032]

[10] The organic EL display device as described in [9], wherein the aforementioned resin containing phenolic hydroxyl groups is polyhydroxystyrene or polyhydroxystyrene / polystyrene copolymer.

[0033] Invention Effects

[0034] Organic EL display devices with high long-term and bending reliability can be obtained, and they will not experience a decrease in luminous brightness or pixel shrinkage due to long-term storage or bending operations. Attached Figure Description

[0035] [ Figure 1 This is a cross-sectional view of a TFT substrate in which a planarization layer and a pixel segmentation layer have been formed.

[0036] [ Figure 2 [Image of a schematic diagram of the substrate for an organic EL display device]

[0037] [ Figure 3 [This is a schematic diagram of the substrate of the organic EL display device used in the bending reliability test based on an embodiment of the present invention.]

[0038] [ Figure 4 [This is a schematic diagram of a bending reliability test based on an embodiment of the present invention.] Detailed Implementation

[0039] The embodiments of the present invention will be described in detail below. It should be noted that the present invention is not limited to the embodiments described below.

[0040] The organic EL display device of the present invention comprises a substrate having a first electrode, a pixel dividing layer, an organic EL layer, and a second electrode on a substrate, and is detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel dividing layer toward the substrate. 75 C4H 12 N + Average ionic strength (I TMA-1 The value is 10.2 × 10 -4 Below 1.0×10 -4 above.

[0041] The inventors of this application conducted repeated and in-depth research, and as a result, determined that by using time-of-flight secondary ion mass spectrometry to detect from the pixel segmentation layer... 75 C4H 12 N + Average ionic strength (I TMA-1 The value is 10.2 × 10 -4 The following can improve the long-term reliability of organic EL display devices. More specifically, this I... TMA-1 Tetramethylammonium ions (TMA) contained in the pixel segmentation layer were identified as causing a decrease in luminous intensity or pixel shrinkage due to the vaporization and leakage of TMA from the pixel segmentation layer into the pixel interior during long-term reliability testing. Since the pixel segmentation layer is in contact with the pixel ends, components that vaporize during long-term reliability testing migrate through the area in contact with the pixel segmentation layer into the pixel segmentation layer, further seeping into the pixel interior, thereby causing pixel shrinkage. Therefore, to improve the long-term reliability of organic EL display devices, it is necessary to quantitatively manage the amount of TMA contained in the pixel segmentation layer. Furthermore, a method for detecting this TMA was discovered... TMA-1 Time-of-flight secondary ion mass spectrometry is suitable.

[0042] From the perspective of improving the long-term reliability of organic EL display devices, I TMA-1 10.2×10 -4 Hereinafter, a preferred setting is 9.6 × 10 -4 The following is a further preferred setting: 8.4 × 10 -4 Hereinafter, a particularly preferred setting is 7.2 × 10 -4 Therefore, there will be no decrease in light intensity or pixel shrinkage, thus providing sufficient long-term reliability for an organic EL display device.

[0043] Furthermore, by making it the aforementioned organic EL display device, and by using time-of-flight secondary ion mass spectrometry to detect the image in the range of 101 nm to 300 nm from the surface of the pixel segmentation layer toward the substrate. 75 C4H12 N + The average value of the ion intensity (I TMA-2 ) is 5.0 x 10 -4 The long-term reliability can be further improved. The I TMA-2 is the TMA ion amount of the inner layer of the pixel division layer. By making the I TMA-1 be in the aforementioned range, the I TMA-2 is made to be 5.0 x 10 -4 or more, the long-term reliability of the organic EL display device can be significantly improved.

[0044] From the viewpoint of improving the long-term reliability of the organic EL display device, the I TMA-2 is preferably 5.0 x 10 -4 or more, more preferably 3.0 x 10 -4 or more, further preferably 2.0 x 10 -4 or more, particularly preferably 1.0 x 10 -4 or more. The lower limit value is not particularly limited and is 0.001 x 10 -4 or more.

[0045] On the other hand, it has also been found that by making the aforementioned I TMA-1 be 1.0 x 10 -4 or more, the bending reliability of the organic EL display device can be improved, and a sufficient bending reliability as an organic EL display device can be imparted. From the viewpoint of improving the bending reliability of the organic EL display device, the I TMA-1 is 1.0 x 10 -4 or more, preferably 3.6 x 10 -4 or more, more preferably 4.5 x 10 -4 or more, further preferably 4.9 x 10 -4 or more, particularly preferably 5.4 x 10 -4 or more, and most preferably 6.0 x 10 -4 or more.

[0046] The decrease in the bending reliability of the organic EL display device is mostly due to the peeling of the pixel division layer from the organic EL pigment. The reason is not clear, but it is believed that by including TMA, the adhesion of the pixel division layer to the organic EL pigment is improved, and thus the peeling of the pixel division layer from the organic EL pigment is less likely to occur, and the bending reliability is improved.

[0047] <Organic EL Display Device>

[0048] The organic EL display device of the present application is an organic EL display device having at least a substrate having a first electrode, a pixel partition layer, an organic EL layer, and a second electrode on a base material. In addition, the organic EL display device of the present application can be an organic EL display device having a plurality of pixels formed on a matrix. As a driving method of the organic EL display device, there are a passive matrix type in which electrodes are divided into columns and rows and only a pixel sandwiched between the electrodes emits light, and an active matrix type in which a plurality of TFTs are provided in each pixel to perform switching, and there is no particular limitation. The organic EL display device of the active matrix type has a TFT (thin film transistor) and a wiring connected to the TFT on a side portion of the TFT on a base material, has a planarization layer in a manner of covering unevenness on a driving circuit thereof, has a first electrode, a pixel partition layer on the planarization layer, and has an organic EL layer and a second electrode.

[0049] Figure 1 A cross-sectional view of an organic EL display device provided on a base material 1 is shown. On the base material 1, a TFT 2 of a bottom gate type or a top gate type is provided in a matrix. A TFT insulating layer 3 is formed in a manner of covering the TFT 2. In addition, a wiring 4 connected to the TFT 2 is provided under the TFT insulating layer 3. Further, on the TFT insulating layer 3, a contact hole 6 opening the wiring 4 is provided, and a planarization layer 5 is provided in a manner of burying them. In the planarization layer 5, an opening portion is provided in a manner of reaching the contact hole 6 of the wiring 4. Further, a first electrode 7 is formed on the planarization layer 5 in a manner of being connected to the wiring 4 via the contact hole 6. Further, a pixel partition layer 8 is formed in a manner of covering a periphery of the first electrode 7. Further, an organic EL layer 9 and a second electrode 10 are formed thereon. The organic EL display device can be a top emission type in which emitted light is emitted from an opposite side of the base material 1, or a bottom emission type in which light is extracted from the base material 1 side.

[0050] [Organic EL display device: substrate]

[0051] The substrate of the organic EL display device of the present application has a unit formed of the aforementioned base material 1, the first electrode 7, and the pixel partitioning portion 8 as the smallest unit. The substrate can also have a configuration including a wiring, a TFT 2, a sensor, a directional antenna, a planarization layer 5, and the like as a driving circuit, as long as it has such a smallest unit. However, in the present application, the components including the wiring, the TFT, the sensor, the directional antenna, and the planarization layer, which are the base of the first electrode, are all treated as part of the substrate. In addition, in a base material having an integrated multifunction such as a sensor for a camera, an ID, a fingerprint reader, an illuminance, a communication, a directional antenna for power supply, and the like in addition to a TFT, it is preferable to provide a planarization layer. By providing the planarization layer, it is possible to cover the unevenness of the wiring, the TFT, and the like before forming the first electrode, thereby planarizing the base material. By planarizing the base material, it is possible to prevent defects in the first electrode and the pixel partitioning layer provided on the base material, thereby obtaining a high-quality substrate.

[0052] Figure 1 The base material 1 in the present application can be appropriately selected from a metal, a glass, a resin film, and the like, which are preferable for the support of the display device and the transportation in subsequent processes. In particular, in cases where flexibility is required, a resin film is preferable.

[0053] As the glass, a soda-lime glass, an alkali-free glass, or the like can be used. The thickness of the glass can be any thickness as long as it is sufficient to maintain mechanical strength. As the material of the glass, an alkali-free glass is preferable because the fewer the eluted ions from the glass, the better. A soda-lime glass to which a barrier coating layer of SiO2or the like is applied can also be used.

[0054] As the material of the resin film, a material containing a resin material selected from the group consisting of a polybenzoxazole resin, a polyamide-imide resin, a polyimide resin, a polyamide resin, and a poly(p-phenylene terephthalate) resin is preferable from the viewpoint of excellent light transmittance. The base material can contain these resin materials alone or in combination.

[0055] For example, in the case of forming the base material using a polyimide resin, it can be formed by applying a solution containing a polyamic acid (including a polyamic acid obtained by partially imidizing) resin, which is a precursor of the polyimide resin, or a soluble polyimide resin to a support substrate and performing a baking process.

[0056] In addition, the aforementioned light-emitting element is known to be fragile in oxygen and moisture, and thus a gas barrier layer can be appropriately provided as a component of the base material. In particular, in the case of a resin film as the base material, the use of an inorganic thin film can provide a display device having high reliability.

[0057] <Organic EL display device: first electrode>

[0058] Regarding the first electrode 7 in this invention, in the case of bottom emission type, it must be a light-transmitting electrode, and in the case of top emission type, it must be a light-reflecting electrode.

[0059] When it is a bottom-emitting type, for example, conductive metal oxides such as transparent tin oxide, indium oxide, and indium tin oxide (ITO) can be used, or metals such as gold, silver, and chromium, inorganic conductive materials such as copper iodide and copper sulfide, conductive polymers such as polythiophene, polypyrrole, and polyaniline, etc., without particular limitation.

[0060] For top-emitting electrodes, materials exhibiting high reflectivity for visible light and low resistance at a certain film thickness are preferred. Furthermore, the material selection must consider its weather resistance in subsequent processes such as wet etching, cleaning, storage, and use. In particular, Ag or Ag alloy films containing Ag as the main component are useful due to their high reflectivity. Ag alloy films such as AgPdCu and AgTiCu, where Ag is the main component, can be used. It is preferable to laminate these Ag alloy films with oxide conductive films such as ITO or IZO films, as this allows for low contact resistance with the organic EL layer. Additionally, Al or Al alloy films containing Al as the main component are also good as the first electrode for top-emitting electrodes. Al-Ni alloy films containing 0.1 to 2 atomic percent Ni have high reflectivity comparable to pure Al and are therefore preferred. Besides these, reflective metal films such as molybdenum (Mo) and tungsten (W) can also be used.

[0061] The first electrode can be formed using known methods. For example, after forming a film using a vacuum film deposition method such as sputtering, it can be patterned by etching using a photoresist.

[0062] Organic EL Display Device: Second Electrode

[0063] In this invention, the second electrode 6 must be a light-reflective electrode in the case of bottom emission type and a light-transmitting electrode in the case of top emission type.

[0064] For bottom-emitting applications, materials exhibiting high reflectivity for visible light and low electrical resistance at a certain film thickness or greater are preferred. Ag or Ag alloy films containing Ag as the main component are useful due to their high reflectivity. MgAg alloys, where Ag is the main component, can be used as Ag alloy films. Additionally, Al or Al alloy films containing Al as the main component are also good as the second electrode for bottom emission. AlCr alloy films containing Cr and AlNi alloy films containing Ni have high reflectivity comparable to pure Al and can achieve low electrical resistance, making them preferred.

[0065] For the top emission type, for example, a transparent conductive metal oxide such as tin oxide, indium oxide, indium tin oxide (ITO), or the like can be used. In order to avoid damage to the organic EL layer, a thin film of an MgAg alloy that can be formed by evaporation is also preferable.

[0066] As for the resistance of the second electrode, as with the first electrode, it is sufficient to supply a current that is sufficient for the light emission of the light emitting element, and thus there is no limitation. From the viewpoint of the power consumption of the light emitting element, a low resistance is desirable. The thickness of the electrode can be arbitrarily selected depending on the characteristics such as the transmittance and the resistance value. For the bottom emission type, a thickness of 100 to 300 nm can be used, and for the top emission type, a thickness of 10 to 30 nm can be used.

[0067] <Organic EL display device: wiring, TFT>

[0068] In the present application, as described above, a wiring, a TFT2, or the like, a drive circuit, is sometimes provided as a member included in the substrate 1.

[0069] As the semiconductor layer of the TFT, a-Si (amorphous silicon), p-Si (polysilicon), microcrystalline silicon, oxides typified by In-Ga-Zn-O, LTPO (Low Temperature Polycrystalline Oxide) in which p-Si and oxides are used together, and the like are generally used, and both a-Si TFTs and p-Si TFTs are commonly used. In the case of the a-Si TFT, the mobility, which is an index of the ease of movement of electrons, is low, but on the other hand, the manufacturing process is relatively short, and it is also possible to manufacture a large substrate, and thus it can be widely used in small to large displays. On the other hand, the p-Si TFT has a high mobility, and it is possible to form a drive circuit or the like on a substrate. The manufacturing process is longer than that of a-Si, and the ease of manufacturing in a large substrate is high, and thus it is preferable to be mainly used in small to medium-sized displays. In particular, p-Si in the p-Si TFT can be generally formed by irradiating laser light to a-Si as a starting film, and instantaneously melting and crystallizing it. In addition, it has a process of doping in which phosphorus or boron is injected into Si, which is not used in the manufacturing process of the a-Si TFT, and threshold control of the characteristics of the TFT can be performed by impurity doping into the Si film.

[0070] <Organic EL display device: organic EL layer>

[0071] The configuration of the organic EL layer 9 in the present application is not particularly limited, and can be, for example, any one of (1) a hole-transporting layer / light-emitting layer, (2) a hole-transporting layer / light-emitting layer / electron-transporting layer, and (3) a light-emitting layer / electron-transporting layer. Furthermore, it can also be a series connection type obtained by stacking a plurality of the aforementioned configurations via a charge generation layer. By making it a series connection type, an increase in luminance and an increase in lifetime of light emission can be expected, and thus it is preferred. The thickness of each layer is preferably 1 nm to 200 nm in view of the influence on the resistance value of the material of each layer and the extraction efficiency of EL light.

[0072] <Organic EL display device: organic EL layer (light-emitting layer)>

[0073] The light-emitting layer is a layer that emits light by exciting a light-emitting material with recombination energy generated by collision of holes and electrons. The light-emitting layer can be a single layer or can be configured by stacking a plurality of layers each formed of a light-emitting material (host material and / or dopant material).

[0074] The light-emitting layer can be formed by a method of co-evaporating a host material and a dopant material, a method of evaporating a host material and a dopant material after mixing them in advance, or the like.

[0075] As the host material that configures the light-emitting layer, for example, there can be mentioned a compound having a condensed aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, tetracene, triphenylene, perylene, fluoranthene, fluorene, indene, and the like. Two or more of them can be used. As the host used when light emission from a triplet state (phosphorescent light emission) is performed in the light-emitting layer, a metal chelated oxinoid compound, a dibenzofuran derivative, a dibenzothiophene derivative, a carbazole derivative, an indolocarbazole derivative, a triazine derivative, a triphenylene derivative, or the like can be preferably used. Among them, a compound having an anthracene skeleton or a pyrene skeleton is easy to obtain high-efficiency light emission, and thus is more preferred.

[0076] As the dopant material constituting the light-emitting material, for example, there can be mentioned fused ring derivatives such as anthracene, pyrene and the like, metal coordination compounds such as tris(8-hydroxyquinoline)aluminum and the like, bistyryl anthracene derivatives, bistyryl benzene derivatives, and the like, tetraphenylbutadiene derivatives, dibenzofuran derivatives, carbazole derivatives, indolocarbazole derivatives, polyphenylenevinylene derivatives, and the like. As the dopant material used when the light-emitting layer performs triplet light emission (phosphorescent light emission), a metal coordination compound containing at least one metal selected from the group consisting of iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re) is preferable. The ligand constituting the metal coordination compound can be appropriately selected depending on the required light emission color, the performance of the organic EL display device, and the relationship with the host compound. The ligand constituting the metal coordination compound preferably has a nitrogen-containing aromatic heterocycle such as a phenylpyridine skeleton, a phenylquinoline skeleton, a carbene skeleton, and the like. Specifically, there can be mentioned tris(2-phenylpyridine)iridium complex, bis(2-phenylpyridine)(acetylacetone)iridium complex, tetraethylporphyrin platinum complex, and the like. Two or more of them can be used.

[0077] <Organic EL display device: organic EL layer (electron transport layer)>

[0078] The electron transport layer is a layer that transports the electrons injected from the cathode to the light-emitting layer. In order to achieve a low driving voltage, the organic EL layer of the present application preferably contains an electron transport layer.

[0079] As the known electron transport material, there is no particular limitation, and there can be mentioned, for example, hydroxyquinoline derivative metal complexes typified by aluminum 8-hydroxyquinolate, benzoquinoline metal complexes, cycloheptatrienone metal complexes, flavonol metal complexes, perylene derivatives, perinone derivatives, naphthalene, anthracene, coumarin derivatives, oxadiazole derivatives, aldehyde azine derivatives, bistyryl derivatives, pyrazine derivatives, phenanthroline derivatives, quinoline derivatives, benzimidazole derivatives, triazole derivatives, quinoxaline derivatives, benzoquinoline derivatives, and the like.

[0080] Among them, from the viewpoint of further reducing the driving voltage and obtaining high-efficiency light emission, a compound having a heteroaryl ring structure containing an electron-accepting nitrogen is preferable. The electron-accepting nitrogen referred to here means a nitrogen atom that forms a double bond with an adjacent atom. Since the nitrogen atom has a high electronegativity, the double bond has the property of electron acceptance. Therefore, the aromatic heterocycle containing the electron-accepting nitrogen has a high electron affinity. The electron transport material having the electron-accepting nitrogen easily accepts electrons from the cathode having a high electron affinity, and thus the driving voltage can be further reduced. In addition, the supply of electrons to the light-emitting layer becomes more, and the recombination probability becomes higher, and thus the light emission efficiency is improved.

[0081] As a heteroaryl ring containing an electron-accepting nitrogen, for example, a triazine ring, a pyridine ring, and the like can be given. As a compound having such a heteroaryl ring structure, from the viewpoint of electron-transporting ability, it is preferable to use a triazole derivative such as N-naphthyl-2,5-diphenyl-l,3,4-triazole, a bipyridine derivative such as 2,5-bis(6'-(2',2"-bipyridyl)) -1,1-dimethyl-3,4-diphenylthiophene, a terpyridine derivative such as 1,3-bis(4'-(2,2':6',2"-terpyridyl)) benzene.

[0082] <Organic EL display device: organic EL layer (charge generation layer)>

[0083] The charge generation layer is usually formed of two layers, and specifically, a pn-junction type charge generation layer formed of an n-type charge generation layer and a p-type charge generation layer can be used. In the case of the above-described pn-junction type charge generation layer, by applying a voltage to the organic EL layer, charges are generated, or charges are separated into holes and electrons, and these holes and electrons are injected into the light-emitting layer via the hole-transporting layer and the electron-transporting layer. Specifically, with respect to a plurality of light-emitting layers included in the organic EL layer, it functions as an intermediate charge generation layer. The n-type charge generation layer supplies electrons to the light-emitting layer present on the anode side, and the p-type charge generation layer supplies holes to the light-emitting layer present on the cathode side. Therefore, it is possible to further improve the light-emitting luminance and the light-emitting efficiency in the organic EL layer including a plurality of light-emitting layers and to reduce the driving voltage, and it is also possible to further improve the light-emitting lifetime of the organic EL layer. For such a reason, in the present application, it is preferable that the organic EL layer include a charge generation layer. Furthermore, as described later, in the present application, it is preferable that the charge generation layer include a donor dopant material. The donor dopant material preferably contains one or more materials selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, inorganic salts of these metals, and complexes of these metals with organic substances.

[0084] The above-described n-type charge generation layer is preferably formed of an n-type dopant material and a host material, and known materials can be used. For example, as the n-type dopant material, an alkali metal, an alkaline earth metal, or a rare earth metal can be used. In addition, as the host material, a compound having a phenanthroline skeleton and a compound having a nitrogen-containing aromatic heterocycle such as an oligopyridine derivative can be used.

[0085] The above-described p-type charge generation layer is preferably formed of a p-type dopant material and a host material, and known materials can be used. For example, as the p-type dopant material, tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), a tetracyanoquinodimethane derivative, an axiophene derivative, iodine, FeCl3, FeF3, SbCl5, and the like can be used. As the p-type dopant material, the axiophene derivative is preferable.

[0086] <Organic EL Display Devices: Organic EL Layer (Hole Transport Layer)>

[0087] Hole transport layers can be formed, for example, by laminating or mixing one or more hole transport materials, or by using a mixture of hole transport materials and polymer binders. Alternatively, inorganic salts such as ferric chloride (III) can be added to the hole transport material to form a hole transport layer. As for the hole transport material, there are no particular limitations as long as it is a compound capable of forming a thin film required for fabricating a light-emitting element, capable of injecting holes from an electrode that serves as the anode, and capable of transporting holes. The hole transport layer can be a single layer or composed of multiple layers.

[0088] Preferred examples of hole transport materials include triphenylamine derivatives such as 4,4'-bis(N-(3-methylphenyl)-N-phenylamino)biphenyl, 4,4'-bis(N-(1-naphthyl)-N-phenylamino)biphenyl, and 4,4',4”-tris(3-methylphenyl(phenyl)amino)triphenylamine, bis(N-allylcarbazole) and other biscarbazole derivatives, pyrazoline derivatives, brunzide compounds, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, phthalocyanine derivatives, porphyrin derivatives and other heterocyclic compounds, as well as polycarbonates, styrene derivatives, polythiophene, polyaniline, polyfluorene, polyvinylcarbazole and polysilanes having the aforementioned monomers on their side chains in polymer systems.

[0089] <Organic EL Display Devices: Planarization Layer>

[0090] Especially for active drive types, in Figure 1 When wiring and TFT2 are provided on substrate 1, planarization layer 5 is preferably used. By providing planarization layer, the unevenness of wiring and TFT2 can be covered to achieve planarization. In this case, in order to provide first electrode 7 on planarization layer, first electrode 7 is preferably connected to wiring and TFT2 through contact holes formed in planarization layer 5. Planarization layer 5 is not limited to any known organic or inorganic material, but from the perspective of processability, a cured film containing a photosensitive resin composition is preferred. Planarization layer 5 can be applied by wet coating methods such as spin coating, slot coating, dip coating, spray coating, and printing, which can uniformly form a thin film on a large substrate.

[0091] Organic EL Display Devices: Pixel Segmentation Layers

[0092] A pixel segmentation layer is a layer that functions to segment pixels, creating openings in the organic EL layer 9 to divide the area into pixels. Specifically, pattern processing is necessary for forming these openings in the pixel segmentation layer, and these pixel openings, acting as removal portions, function as display pixels. Furthermore, the pixel segmentation layer serves to electrically insulate adjacent pixels from each other; therefore, it must be an insulating organic or inorganic material, not limited to either. However, from a pattern processing perspective, a cured film of a photosensitive resin composition is preferred.

[0093] The pixel segmentation layer I of the present invention TMA-1 10.2×10 -4 Below 1.0×10 -4 The above achieves both long-term reliability and bending reliability.

[0094] As for making the aforementioned I TMA-1 10.2×10 -4 Below 1.0×10 -4 The above methods can be exemplified by methods 1 through 3. It should be noted that the method used to make I... TMA-1 10.2×10 -4 Below 1.0×10 -4 The above methods are not particularly limited, but method 1 may adversely affect the storage stability of the photosensitive resin composition due to the anionic components contained in the TMA compound. Therefore, methods 2 and 3 are preferred. From the perspective of further simplifying the manufacturing process, method 3 is particularly preferred. That is, for the organic EL display device of the present invention, it is preferable that the pixel segmentation layer, in the infrared spectrophotometer measured using a Fourier transform infrared spectrophotometer (FT-IR), has a value at 1365 cm⁻¹. -1 Above 1385cm -1 The index A, which is maximal within the range below, indicates the amount of imide structure contained in the pixel segmentation layer, being greater than 0.10 and less than 1.10.

[0095] [Method 1]

[0096] Method 1 is as follows: A TMA compound is added to a photosensitive resin composition used to form a pixel segmentation layer; the aforementioned photosensitive resin composition is used to form a pixel segmentation layer, thereby enabling I... TMA-1 At 10.2×10 -4 Below 1.0×10 -4 Within the above range. More specifically, by adding a TMA compound to the photosensitive resin composition used to form the pixel segmentation layer and adjusting the amount added, the amount of TMA remaining in the cured pixel segmentation layer can be adjusted, thereby enabling I... TMA-1 At 10.2×10 -41.0 x 10 -4 The above range. As a specific example of the TMA compound, tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, and the like can be given.

[0097] [Method 2]

[0098] Method 2 is a method in which I TMA-1 is 10.2 x 10 -4 After the above pixel division layer, the pixel division layer is washed with an acidic aqueous solution, thereby reducing the TMA ions in the pixel division layer, and I TMA-1 is 10.2 x 10 -4 The above range. More specifically, I -4 is 10.2 x 10 TMA-1 is 10.2 x 10 -4 The above cured pixel division layer is immersed in an acidic aqueous solution for 2 minutes, and then rinsed with distilled water, whereby the TMA ions in the pixel division layer can be reduced, and I TMA-1 is 10.2 x 10 -4 The above range. More specifically, I -4 The above. As the acidic aqueous solution washing method, a method using spray, spin immersion, immersion, or the like of an acidic aqueous solution can be given. As the acidic aqueous solution, a weak acid having a pH of 3.0 or more and less than 6.0 is preferred. In the case of using a strong acid having a pH of less than 3.0, the washing action becomes too strong, and I TMA-1 becomes too low, and thus is not preferred. Specifically, an aqueous solution of oxalic acid, sulfurous acid, phosphoric acid, nitrous acid, hydrofluoric acid, formic acid, benzoic acid, acetic acid, antimony acid, carbonic acid, or the like is adjusted so as to have a pH in the above range and used.

[0099] [Method 3]

[0100] Method 3 is a method in which the pixel division layer has a maximum in the range of 1365 cm -1 or more and 1385 cm -1 and the index A indicating the amount of existence of the imide structure contained in the pixel division layer is 0.10 or more and 1.10 or less.

[0101] Index A = (Maximum value in the range of 1365 cm -1 or more and 1385 cm -1 ) / (Maximum value in the range of 1590 cm -1 or more and 1610 cm -1 )

[0102] (wherein, the maximum value used in the above index A is the intensity value of the absorption maximum measured by FT-IR.)

[0103] This method allows TMA ions from a tetramethylammonium hydroxide (TMAH) aqueous solution used in the development process after pattern exposure of the photosensitive resin composition to permeate into the film during this process. By keeping the aforementioned index A within the aforementioned range, the permeation of TMA ions becomes appropriate, resulting in the ability to permeate the I of the pixel segmentation layer. TMA-1 10.2×10 -4 Below 1.0×10 -4 The above. In the infrared spectra measured using a Fourier transform infrared spectrophotometer (FT-IR), at 1365 cm⁻¹... -1 Above 1385cm -1 Within the following range, there is absorption from the imide structure. In method 3, the pixel segmentation layer must contain an imide structure. Furthermore, the aforementioned index A is essentially an indicator of the amount of imide structure contained in the pixel segmentation layer. As a method to make index A between 0.10 and 1.10, it can be achieved by including an imide structure in the pixel segmentation layer and setting the amount of imide structure within a specific range.

[0104] Furthermore, for the pixel segmentation layer of the present invention, by making I TMA-2 5.0×10 -4 The following can further improve long-term reliability. As a result, I... TMA-2 5.0×10 -4 The following methods are examples, without any particular limitation.

[0105] This allows for detection using time-of-flight secondary ion mass spectrometry within a range of 20 nm to 300 nm from the surface of the pixel segmentation layer towards the substrate. 31 CF + Average ionic strength (I CF ) is 0.5×10 -4 The following method. By making I CF 0.5×10 -4 The following can suppress the penetration of TMA ions during development, resulting in I TMA-2 5.0×10 -4 The following describes a preferred organic EL display device, specifically one where time-of-flight secondary ion mass spectrometry is used to detect the image within a range of 20 nm to 300 nm from the pixel segmentation layer surface toward the substrate. 31 CF + Average ionic strength (I CF ) is 0.5×10 -4The following. More specifically, it is preferable that the photosensitive resin composition used for forming the pixel division layer does not contain a fluorine atom. The lower limit value is not particularly limited, and is 0.001 x 10 -4 The above.

[0106] <Pixel division layer: imide>

[0107] The pixel division layer of the present application preferably contains an imide structure. By causing the pixel division layer of the present application to contain a specific amount of imide structure, it is possible to make the aforementioned I TMA-1 In a specific range, thereby improving long-term reliability and bending reliability. As a method of measuring whether or not the pixel division layer contains polyimide, for example, a method of analyzing the pixel division layer using FT-IR can be given. In the case where the pixel division layer contains polyimide, in the infrared spectrogram measured using FT-IR, a peak at 1365 cm -1 The above 1385 cm -1 The following range has a very large value, and therefore, it can be judged depending on the presence or absence of the large value. In addition, in the present application, an index A indicating the amount of presence of the imide structure contained in the pixel division layer is defined. From the fact that the aforementioned I TMA-1 From the viewpoint of the fact that the aforementioned I TMA-1 From the viewpoint of the fact that the aforementioned I

[0108] Index A = (1365 cm -1 The above 1385 cm -1 The maximum value in the following) / (1590 cm -1 The above 1610 cm -1 The maximum value in the following)

[0109] (wherein the maximum value used in the aforementioned index A is the intensity value of the absorption maximum measured using FT-IR.)

[0110] As a method of making the aforementioned index A 0.10 or more and 1.10 or less, it is possible to achieve this substantially by adjusting the amount of imide structure contained in the photosensitive resin composition used to form the pixel division layer. More specifically, it is possible to achieve this by forming the pixel division layer using a photosensitive resin composition in which the molar amount of imide structure contained in the entirety of the components of the photosensitive resin composition excluding the solvent is 0.2 mmol / g or more and 0.9 mmol / g or less. The molar amount (mmol / g) of imide structure contained in the entirety of the components of the photosensitive resin composition excluding the solvent can be calculated from the calculated value of the imide structure contained in the entirety of the components of the photosensitive resin composition excluding the solvent.

[0111] By increasing the amount of components other than polyimide, polybenzoxazole described later, and a resin containing a phenolic hydroxyl group, which are contained in the polyimide-based photosensitive resin composition, it is possible to make the molar amount of imide structure 0.2 mmol / g or more and 0.9 mmol / g or less, using the calculated value of the molar amount of imide structure described above, and as a result, make the aforementioned index A 0.10 or more and 1.10 or less.

[0112] <Pixel division layer: benzoxazole>

[0113] The pixel division layer of the present application preferably contains a benzoxazole structure. By making the pixel division layer of the present application contain a benzoxazole structure, it is possible to efficiently reduce the value of index A of the pixel division layer. As a method of determining whether or not the pixel division layer contains a benzoxazole structure, for example, a method of analyzing the pixel division layer using FT-IR can be given. In the case where the pixel division layer contains a benzoxazole structure, in the infrared spectrum determined using FT-IR, a large peak is present at 1040 cm -1 A large peak is present in the range of 1060 cm -1 Therefore, it is possible to determine this based on the presence or absence of a large peak. In the present application, an index B indicating the amount of benzoxazole structure contained in the pixel division layer is defined. This index B is an index indicating the amount of imidazole structure relative to the amount of imide structure, and by making the value of this index within a specific range, it is possible to improve the crack resistance of the organic EL display device. From the viewpoint of improving the crack resistance of the organic EL display device, the index B is preferably 0.20 or more, more preferably 0.30 or more, further preferably 0.40 or more, and particularly preferably 0.50 or more. From the viewpoint of achieving a balance in long-term reliability, the index B is preferably 2.50 or less, more preferably 2.00 or less, further preferably 1.80 or less, and particularly preferably 1.50 or less.

[0114] Index B = (1040 cm -1 A large peak is present in the range of 1060 cm -1maxima in the range of 1,300 to 1,400 cm"1) / (1365 cm"1) -1 maxima in the range of 1,300 to 1,400 cm"1) / (1365 cm"1) -1 maxima in the range of 1,300 to 1,400 cm"1) / (1365 cm"1)

[0115] (wherein the maxima used in the above index B is the intensity value of the absorption maxima measured by FT-IR).

[0116] That is, for the organic EL display device of the present application, it is preferable that the pixel partition layer have a maxima in the infrared spectrum measured by FT-IR in the range of 1,040 to 1,060 cm"1 -1 maxima in the range of 1,300 to 1,400 cm"1) / (1365 cm"1) -1 maxima in the range of 1,300 to 1,400 cm"1) / (1365 cm"1)

[0117] The reason is not clear, but it is presumed as follows: by making the ratio of the imide structure to the oxazole structure contained in the pixel partition layer within a certain range, so that the intermolecular interaction of each of the imide structure and the oxazole structure does not become too strong, the brittleness resulting from the too strong intermolecular interaction is moderated, as a result, the pixel partition layer can be imparted with moderate flexibility, and the crack resistance is improved. As a method for making the index B 0.20 to 2.50, the addition ratio of the polyimide and / or the polyimide precursor, the polybenzoxazole and / or the polybenzoxazole precursor, and other components can be adjusted, thereby making the aforementioned index B 0.20 to 2.50.

[0118] <Compound from a resin containing a phenolic hydroxyl group>

[0119] The pixel partition layer of the present application preferably contains a compound from a resin containing a phenolic hydroxyl group. In order to make the pixel partition layer contain a compound from a resin containing a phenolic hydroxyl group, the photosensitive resin composition used for forming the pixel partition layer must substantially contain a resin containing a phenolic hydroxyl group. By making the aforementioned photosensitive resin composition contain a resin containing a phenolic hydroxyl group, the content of the imide structure in the aforementioned photosensitive resin composition is relatively reduced, and the amount of TMA permeating into the pixel partition layer at the development process after the pattern exposure of the photosensitive resin composition during the formation of the pixel partition layer can be controlled. As a result, the amount of the TMA ion remaining in the pixel partition layer after curing can be reduced, and the long-term reliability can be easily improved. In addition, the resin containing a phenolic hydroxyl group easily forms a crosslinked structure with the crosslinking agent described later, and the crack resistance of the pixel partition layer can be easily improved. As a method for determining whether the pixel partition layer contains a compound from a resin containing a phenolic hydroxyl group, for example, pyrolysis GC / MS can be used, in which the pixel partition layer is subjected to pyrolysis at 600°C, and then the components are measured by gas chromatography.

[0120] The content of the compound from the resin containing phenolic hydroxyl group is preferably 1% by mass or more and 50% by mass or less in 100% by mass of the pixel division layer.

[0121] <Compound from thermal acid generator in pixel division layer>

[0122] The pixel division layer of the present application preferably contains a compound from a thermal acid generator. In order to make the pixel division layer contain a compound from a thermal acid generator, the photosensitive resin composition used for forming the pixel division layer must substantially contain a thermal acid generator. By making the aforementioned photosensitive resin composition contain a thermal acid generator, an acid is generated in the curing step of the pixel division layer, and it is easy to cause the TMA ion contained in the pixel division layer to undergo thermal cleavage, and therefore, as a result, it is possible to reduce the amount of the TMA ion remaining in the pixel division layer after curing, and it is easy to improve long-term reliability.

[0123] The content of the compound from the thermal acid generator is preferably 0.1% by mass or more and 10% by mass or less in 100% by mass of the pixel division layer. When it is 0.1% by mass or more and 10% by mass or less, it is easy to obtain the effect of causing the TMA ion contained in the pixel division layer to undergo thermal cleavage.

[0124] <Photosensitive resin composition for forming pixel division layer>

[0125] Next, the photosensitive resin composition for forming the pixel division layer of the present application is described.

[0126] The pixel division layer of the present application is preferably a cured film of a photosensitive resin composition capable of being subjected to patterning processing. From the viewpoint of patterning properties and reliability, the photosensitive resin composition for forming the pixel division layer of the present application can be obtained by dissolving an alkali-soluble resin, a quinonediazide compound, a thermal acid generator, a thermal crosslinking agent, an organic solvent, an adhesion improver, a surfactant, and a colorant, and the like.

[0127] Next, the components contained in the photosensitive resin composition for forming the pixel division layer of the present application are described. The photosensitive resin composition for forming the pixel division layer of the present application can contain a polyimide, a polybenzoxazole, a resin containing phenolic hydroxyl group, a polymer obtained by polymerizing a radically polymerizable monomer, a Cardo resin, and a polysiloxane, and the like, among which, a resin having alkali solubility is preferably used.

[0128] In the present application, the alkali solubility means that a solution obtained by dissolving a resin in γ-butyrolactone is applied to a silicon wafer, prebaked at 120°C for 4 minutes to form a prebaked film having a film thickness of 10 μm ± 0.5 μm, and after the prebaked film is immersed in a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 23 ± 1°C for 1 minute, the film thickness is reduced by rinsing with pure water, and the dissolution rate obtained from the film thickness at this time is 50 nm / minute or more.

[0129] <Photosensitive resin composition: polyimide>

[0130] In order to impart an imide structure to the pixel division layer, it is virtually meant that the photosensitive resin composition used for forming the pixel division layer contains a polyimide and / or a polyimide precursor, which can use a substance synthesized by a known method.

[0131] In the case of a polyimide precursor, if it is a polyamic acid, it can be synthesized by, for example, a method in which tetracarboxylic dianhydride is reacted with a diamine compound at a low temperature, and if it is a polyamic acid ester, it can be synthesized by, for example, a method in which tetracarboxylic dianhydride is reacted with a diamine compound at a low temperature, and then the amic acid structure is partially esterified by using N,N-dimethylformamide dimethyl acetal or the like; a method in which diester is obtained from tetracarboxylic dianhydride and alcohol, and then reacted in the presence of an amine and a condensing agent; a method in which diester is obtained from tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is subjected to acyl chloride treatment, and reacted with an amine.

[0132] In the case of a polyimide, it can be obtained by, for example, a method in which the polyamic acid or polyamic acid ester obtained by the aforementioned method is subjected to dehydration ring closure in an organic solvent by heating or chemical treatment with an acid, a base, or the like.

[0133] As the acid dianhydride used as a raw material of the polyimide and / or the polyimide precursor, specifically, there can be mentioned aromatic tetracarboxylic dianhydride such as 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, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, aliphatic tetracarboxylic dianhydride such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and tetracarboxylic dianhydride having the structure shown below, and the like. Two or more of them can be used.

[0134] [Chemical Formula 3]

[0135]

[0136] R 4 represents an oxygen atom, SO2, a ring, C(CF3)2, C(CH3)2, or a hydrocarbon group. R 5 ~R 8 each independently represents a hydrogen atom, or a hydroxyl group.

[0137] As specific examples of the diamine used as a raw material for the polyimide, the polyimide precursor, and the copolymer containing them, 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, 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 a compound in which at least a part of the hydrogen atoms of the aromatic rings thereof are substituted with alkyl groups, halogen atoms, aliphatic cyclohexanediamine, methylenebiscyclohexylamine, and a diamine having the structure shown below, or the like can be used. Two or more of them can be used.

[0138] [Chemical Formula 4]

[0139]

[0140] R 9 , R 12 represents an oxygen atom, SO2, a ring, C(CF3)2, or C(CH3)2, or a hydrocarbon group. R 10 , R 11 , R 13 ~R 20 each independently represents a hydrogen atom, or a hydroxyl group.

[0141] In the present application, the polyimide is defined as a resin having an imide bond in the main chain. Note that, in the case where the polyimide contains a structural unit of a polyimide and / or a structural unit of a polyimide precursor, and also contains a structural unit of a polybenzoxazole and / or a structural unit of a polybenzoxazole precursor, it is regarded as a polyimide.

[0142] <Photosensitive resin composition: polybenzoxazole>

[0143] In order to make the pixel division layer have a benzoxazole structure, it substantially means that the photosensitive resin composition used for forming the pixel division layer contains a polybenzoxazole and / or a polybenzoxazole precursor, and a substance synthesized using a known method can be used.

[0144] In the case of the polybenzoxazole precursor, as a production method, it can be obtained by subjecting a bisaminophenol compound to a condensation reaction with a dicarboxylic acid. Specifically, there are a method of reacting a dehydration condensing agent such as dicyclohexyl carbodiimide (DCC) with an acid and adding a bisaminophenol compound thereto, a method of dropping a solution of a diacyl chloride into a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added, and the like.

[0145] In the case of the polybenzoxazole, it can be obtained by, for example, subjecting the polybenzoxazole precursor obtained by the aforementioned method to dehydration ring closure in an organic solvent by heating or chemical treatment with an acid, a base, or the like.

[0146] As examples of the dicarboxylic acid used as a raw material of the benzoxazole and / or the benzoxazole precursor, there are terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, diphenyl dicarboxylic acid, benzophenone dicarboxylic acid, trisphenyl dicarboxylic acid, and the like, as examples of the tricarboxylic acid, there are trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, and the like, as examples of the tetracarboxylic acid, there are 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-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene, and the like aromatic tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, and the like aliphatic tetracarboxylic acid. Two or more of them can be used.

[0147] In addition, in order to improve the storage stability of the photosensitive resin composition, it is preferable that an end capping agent such as a monoamine, an anhydride, a monocarboxylic acid, a monoacyl chloride compound, a monoactive ester compound, or the like, is used to cap the main chain terminal of one or more alkali-soluble resins selected from the group consisting of a polyimide, a polyimide precursor, a polybenzoxazole, a polybenzoxazole precursor, and a copolymer thereof. In order to improve the chemical resistance of the resin cured product obtained by performing the baking, as the end capping agent, a monoamine, an anhydride, a monocarboxylic acid, a monoacyl chloride compound, a monoactive ester compound having at least one alkenyl group or alkynyl group can be used.

[0148] The content of the end capping agent such as a monoamine, an anhydride, an acyl chloride, a monocarboxylic acid, or the like, is preferably 1 mol% or more, and more preferably 5 mol% or more, relative to 100 mol% of the total of all monomer components constituting the resin, from the viewpoint of improving the storage stability. In addition, it is preferably 40 mol% or less, and more preferably 30 mol% or less, relative to 100 mol% of the total of all monomer components constituting the resin, from the viewpoint of obtaining a resin having good film properties. A plurality of different terminal groups can be introduced by allowing a plurality of end capping agents to react.

[0149] <Photosensitive resin composition: polyimide and polybenzoxazole>

[0150] In the present application, it is preferable that the aforementioned pixel division layer contains a polyimide and / or a polybenzoxazole having a structure represented by Formula (1). It is possible to further reduce I TMA-2 , and furthermore, it is possible to further reduce I TMA-1 .

[0151] [Chemical Formula 5]

[0152]

[0153] In Formula (1), X 1 represents a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms, R 1 each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and a each independently represents an integer of 0 to 4.

[0154] The aforementioned X 1 is a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms. By making X 1 a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms, the hydrophobicity of the polyimide and / or the polybenzoxazole is improved, and the penetration of TMA ions can be efficiently suppressed. On the other hand, in the case of including a cyclic structure, the steric volume is large, and therefore, in the development process, TMA ions easily penetrate into the pixel division layer, and thus, it is not preferable.

[0155] It is particularly preferable to make X1 is a structure represented by formula (2). Hydrophobicity can be more efficiently improved, and thus I TMA-2 .

[0156] [Chemical Formula 6]

[0157]

[0158] In formula (2), R 2 and R 3 each independently represents a non-cyclic hydrocarbon group having 1 to 9 carbon atoms or a hydrogen atom, represents a bonding site bonded to an aromatic ring. Note that R 2 and R 3 have a total of 3 to 9 carbon atoms.

[0159] As a specific example of the structure of the aforementioned X 1 , the following structures and the like can be given, but are not limited thereto. In addition, from the viewpoint of easily improving the solvent solubility of the polyimide and the polybenzoxazole, it is preferable that the structures of R 2 and R 3 be different from each other.

[0160] [Chemical Formula 7]

[0161]

[0162] <Photosensitive resin composition: resin containing phenolic hydroxyl group>

[0163] In order to make the pixel division layer contain a compound from a resin containing a phenolic hydroxyl group, it substantially means that a photosensitive resin composition for forming the pixel division layer contains a resin containing a phenolic hydroxyl group, and they can use a substance synthesized by a known method.

[0164] The resin containing a phenolic hydroxyl group in the present application is a resin having a phenolic hydroxyl group, a naphthol structure as a structural unit, for example, a polyhydroxystyrene resin, a Novolac resin, a Resol resin, a triphenol type phenol resin, and a biphenylene methylene type phenol resin can be given, but are not limited thereto.

[0165] The polyhydroxystyrene resin can be obtained, for example, by addition polymerization of a phenol derivative having an unsaturated bond by a known method. As the phenol derivative having an unsaturated bond, for example, a hydroxystyrene, a dihydroxystyrene, an allyl phenol, a coumaric acid, a 2'-hydroxychalcone, a resveratrol, a 4-hydroxystilbene, and the like can be given, and two or more kinds thereof can be used. In addition, it can also be a copolymer with a monomer not containing a phenolic hydroxyl group such as styrene.

[0166] The novolac resin, the resol resin, and the benzyl ether type phenol resin can be obtained by subjecting phenols and aldehydes and the like to polycondensation using known methods.

[0167] As the phenols, for example, 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, methylene bisphenol, methylene bis(p-cresol), resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butyloxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, a-naphthol, β-naphthol, and the like can be given. Two or more of them can be used.

[0168] Further, as the aldehydes, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like can be given. Two or more of them can be used.

[0169] The biphenylylene methylene type phenol resin can be obtained by subjecting the above-mentioned phenols to polycondensation with bischloromethyl biphenyl.

[0170] Among them, from the viewpoint of easily reducing the I TMA-1 of the pixel division layer, polyhydroxystyrene, polyhydroxystyrene / polystyrene copolymer, and biphenylylene methylene type phenol resin are preferred. From the viewpoint of further easily reducing the I TMA-1 of the pixel division layer, polyhydroxystyrene and polyhydroxystyrene / polystyrene copolymer are further preferred. The resin containing phenolic hydroxyl group is more preferably polyhydroxystyrene or polyhydroxystyrene / polystyrene copolymer.

[0171] <Photosensitive resin composition: other resins>

[0172] The photosensitive resin composition used for forming the pixel division layer of the present application can also contain a polymer obtained by polymerizing a radically polymerizable monomer, a Cardo resin, and a polysiloxane within a range not impairing the effects of the present application.

[0173] As the polymer obtained by polymerizing the radical polymerizable monomer, a polymer obtained by radical polymerization of (meth)acrylic acid, (meth)acrylate is preferable. As the (meth)acrylate, known monomers 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-cyclopropyloxy carbonyl ethyl (meth)acrylate, 2-cyclopentyloxy carbonyl ethyl (meth)acrylate, 2-cyclohexyloxy carbonyl ethyl (meth)acrylate, 2-cyclohexenyl oxy carbonyl ethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxy carbonyl ethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, adamantylmethyl (meth)acrylate, 1-methyladamantyl (meth)acrylate, and the like can be used. Here, the (meth)acrylic acid is a general term for methacrylic acid and acrylic acid, and the same applies to the compounds in the present specification including the above series of compounds. Styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, and the like can be copolymerized with the above (meth)acrylic acid, (meth)acrylate. In addition, an olefinically unsaturated double bond group can be introduced by addition reaction of an epoxy compound having an olefinically unsaturated double bond group with (meth)acrylic acid.

[0174] As the Cardo resin, a resin 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, can be exemplified. The Cardo structure is generally a structure in which two aromatic rings are bonded to the 9-position of a fluorene ring. As a specific example of the skeleton structure in which two ring structures are bonded to a quaternary carbon atom constituting a ring structure, a bis-arylfluorene skeleton, a bis-phenol fluorene skeleton, a bis-amino phenyl fluorene skeleton, and the like can be exemplified. An epoxy group, an acrylic group, a methacrylic group, or the like can also be present as a substituent on the aforementioned skeleton. The Cardo resin can be formed by polymerization through a reaction between functional groups having a skeleton having the Cardo structure bonded thereto, or the like. The Cardo resin has a structure in which a main chain and a bulky side chain are connected by one element (Cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain. As a specific example of a monomer having a Cardo structure, a bis(glycidyloxyphenyl) fluorene type epoxy resin, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and the like can be exemplified. The Cardo resin is a polymer obtained by polymerizing a monomer having a Cardo structure, and can also be a copolymer with other copolymerizable monomers.

[0175] As the polysiloxane, for example, a siloxane resin obtained by hydrolyzing one or more selected from the group consisting of 4-functional organosilane, 3-functional organosilane, 2-functional organosilane, and 1-functional organosilane (sometimes referred to as monomers of siloxane resin) and partially condensing it by dehydration reaction can be mentioned. The operation of partially condensing it by dehydration reaction is sometimes simply referred to as partially condensing it. As specific examples of the organosilane, 4-functional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxy silane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 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)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [((3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [((3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 3-functional silanes, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, di(1-naphthyl)diethoxysilane, 2-functional silanes, trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 1-functional silanes, can be mentioned. Two or more of these organosilanes can be used. In addition, a silicate compound such as Methyl Silicate 51 manufactured by Fuso Chemical Co., Ltd., M Silicate 51 manufactured by Tama Chemical Co., Ltd., and the like can be copolymerized.

[0176] The polysiloxane can be synthesized by subjecting a monomer of polysiloxane such as organosilane to hydrolysis and partial condensation. Here, the so-called partial condensation means that not all of the Si-OH of the hydrolyzate is condensed, and a part of the Si-OH remains in the obtained polysiloxane. In the hydrolysis and partial condensation, a usual method can be used. For example, a method of adding an organic solvent, water, a catalyst as needed, to a mixture of organosilane, and performing heating stirring at 50 to 150°C for about 0.5 to 100 hours, and the like can be mentioned. In the stirring, as needed, the hydrolysis by-product (alcohol such as methanol), the condensation by-product (water) can be removed by distillation.

[0177] The catalyst at the time of subjecting a monomer of polysiloxane such as organosilane to hydrolysis and partial condensation is not particularly limited, and an acid catalyst, a base catalyst is preferably used. As a specific example of the acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, a polybasic carboxylic acid or an acid anhydride thereof, an acid cation exchange resin, and the like can be mentioned. As a specific example of the base catalyst, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, an alkoxysilane having an amino group, a basic anion exchange resin, and the like can be mentioned.

[0178] <Photosensitive resin composition: thermal acid generator>

[0179] In order to make the pixel division layer contain a compound from the thermal acid generator, the photosensitive resin composition for forming the pixel division layer must substantially contain the thermal acid generator.

[0180] The thermal acid generator has a function of generating an acid by heating, and a compound having a function of generating an acid by light such as ultraviolet light in addition to heat is also included in the definition of the thermal acid generator. However, in the case of a quinonediazide compound, even in the case of generating an acid by heating, it is defined as a compound not included in the thermal acid generator.

[0181] As the thermal acid generator, a sulfonium salt, a sulfonate, and the like can be mentioned. Two or more of them can be contained.

[0182] The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid, benzene sulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or camphorsulfonic acid, and the like is preferred.

[0183] Among the thermal acid generators, from the viewpoint of the effect of improving long-term reliability, a thermal acid generator containing a sulfonic acid ester structure is preferred. Examples of the thermal acid generator containing a sulfonic acid ester structure include compounds obtained by sulfonating a compound containing an alcoholic hydroxyl group or a compound containing a phenolic hydroxyl group with methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, or the like. Examples of the compound containing an alcoholic hydroxyl group include methanol, ethanol, propanol, butanol, and examples of the phenolic hydroxyl group include phenol, cresol, naphthol, and the like. In addition, examples of the 2-membered alcohol compound include methanediol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and the like. Examples of the 3-membered or higher alcohol compound include glycerol, erythritol, pentaerythritol, and the like. Examples of the polyhydric phenol compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, and the like.

[0184] Examples of the thermal acid generator having a function of generating acid using light such as ultraviolet light in addition to heat include "Irgacure" PAG103, PAG121 (trade name, manufactured by BASF Japan, Ltd.), PA-411, PA-480 (trade name, manufactured by Heraeus, Ltd.), PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, PAI-1004 (trade name, manufactured by Midori Kagaku, Ltd.), SP-082, SP-601, SP-606, SP-607, SP-612 (trade name, manufactured by ADEKA Corporation), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (trade name, manufactured by Heraeus, Ltd.), NAI-105, NAI-106, NAI-109 (trade name, manufactured by Midori Kagaku, Ltd.), and the like.

[0185] <Photosensitive resin composition: quinonediazide compound>

[0186] For the purpose of imparting pattern processability, the photosensitive resin composition used for forming the pixel division layer of the present application preferably contains a quinonediazide compound. By containing a quinonediazide compound, an acid is generated at the light-irradiated portion, the solubility of the light-irradiated portion in an alkaline aqueous solution increases, and a positive type relief pattern in which the light-irradiated portion is dissolved can be obtained. As the quinonediazide compound, a compound obtained by bonding a quinonediazidosulfonyl group to a polyhydroxy compound in the form of an ester, a compound obtained by bonding a quinonediazidosulfonyl group to a polyamino compound in the form of a sulfonamide bond, a compound obtained by bonding a quinonediazidosulfonyl group to a polyhydroxy polyamino compound in the form of an ester bond and / or a sulfonamide bond, and the like can be mentioned. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds be substituted with a quinonediazido group. In addition, the photosensitive resin composition can contain two or more kinds of quinonediazide compounds.

[0187] Among the quinonediazide compounds, it is preferable to use a naphthoquinonediazidosulfonic acid ester compound, which can be synthesized by esterification of a compound having a phenolic hydroxyl group with a naphthoquinonediazidosulfonic acid compound, and which can be synthesized using a known method. By using these naphthoquinonediazidosulfonic acid ester compounds, the resolution, sensitivity, and residual film rate are further improved.

[0188] As the compound having a phenolic hydroxyl group as used herein, there can be mentioned 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, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Hokuriku 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, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacyloxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Hokuriku Chemical Industry Co., Ltd.), and the like. As the naphthoquinonediazide sulfonic acid ester compound, there can be mentioned, as a preferable example, a compound obtained by introducing a diazido naphthoquinone-4-sulfonic acid or a diazido naphthoquinone-5-sulfonic acid via an ester bond to these compounds, but a compound other than these can also be used.

[0189] The diazido naphthoquinone-4-sulfonic acid ester compound has an absorption in the i-ray region of a mercury lamp, and is suitable for i-ray exposure, and the absorption of the diazido naphthoquinone-5-sulfonic acid ester compound extends to the g-ray region of a mercury lamp, and is suitable for g-ray exposure. The pixel division layer of the present application can contain any of the diazido naphthoquinone-4-sulfonic acid ester compound and the diazido naphthoquinone-5-sulfonic acid ester compound, can contain a naphthoquinonediazide sulfonic acid ester compound in which a diazido naphthoquinone-4-sulfonyl group and a diazido naphthoquinone-5-sulfonyl group are used in the same molecule, and can contain a mixture of the diazido naphthoquinone-4-sulfonic acid ester compound and the diazido naphthoquinone-5-sulfonic acid ester compound.

[0190] <Photosensitive resin composition: thermal crosslinking agent>

[0191] The photosensitive resin composition used for forming the pixel division layer of the present application can contain a thermal crosslinking agent. The thermal crosslinking agent refers to a compound having a functional group such as a hydroxymethyl group, an alkoxymethyl group, an epoxy group, or an oxetanyl group, which is thermally reactive. The thermal crosslinking agent can crosslink the resin or other additive ingredients, thereby improving the chemical resistance and heat resistance of the pixel division layer.

[0192] As the thermal crosslinking agent having a hydroxymethyl group and / or an alkoxymethyl group, for example, DML-PC, DML-PEP, DMOM-PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP, HMOM-TPPA (all trade names, manufactured by Hokuriku Chemical Industry Co., Ltd.), 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), "NIKALAC" (registered trademark) MX-290, MX-280, MX-270, MX-279, MW-100LM, MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), and the like can be mentioned, and are available from each of the above companies, respectively.

[0193] As the thermal crosslinking agent having an epoxy group, "Epikote" (registered trademark) 807, 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250, E4275 (all of which are trade names, manufactured by Japan Epoxy (Co., Ltd.), "Epiclon" (registered trademark) EXA-4880, EXA-4822, EXA-9583, HP4032, HP4770 (all of which are trade names, manufactured by Daiichi Ink Chemical Industry (Co., Ltd.), "EPOLIGHT" (registered trademark) 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 80MF, 4000, 3002, 1708A, 1608F (all of which are trade names, manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, EX-214L, EX-216L, EX-252, EX-850L, EX-201-IM, EX-321L, EX-614B, EX-313, EX-512, EX-321L, EX-810, EX-861, EX-211 (all of which are trade names, manufactured by Nagase Chemtex Corporation), GAN, GOT (all of which are trade names, manufactured by Nippon Kayaku Co., Ltd.), "Celloxide" (registered trademark) 2021P (trade name, manufactured by DAICEL), "RIKARESIN" (registered trademark) DME-100, BEO-60E (all of which are trade names, manufactured by Shin Nippon Rika Co., Ltd.), "TBIS" (registered trademark) -GG, -RXG, -BNEG (trade names, manufactured by Taguchi Chemical Industry Co., Ltd.), VG3101L (trade name, manufactured by PrintTech Corporation), "TEPIC" (registered trademark) -S, -L, -VL, -FL, -UC (all of which are trade names, manufactured by Nissan Chemical Industries, Ltd.), "Epiclon" N660, N695, HP7200 (all of which are trade names, manufactured by Daiichi Ink Chemical Industry (Co., Ltd.), NC6000, EPPN502H, NC3000 (all of which are trade names, manufactured by Nippon Kayaku Co., Ltd.), "Epotohto" (registered trademark) YH-434L (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), EHPE-3150 (trade name, manufactured by DAICEL), MA-DGIC (trade name, manufactured by Shikoku Chemicals Corporation), "EPOCHALIC" (registered trademark) THI-DE, DE-102, DE-103 (all of which are trade names, manufactured by ENEOS Corporation), "Shofree" (registered trademark) CDMDG (trade name, manufactured by Showa Denko K.K.), "Epogosei" (registered trademark) BD, NPG, HD (all of which are trade names, manufactured by Yuka Syoki Co., Ltd.), and the like can be respectively obtained from each company.

[0194] As the oxetane compounds, for example, OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all are trade names, manufactured by Toagosei Co., Ltd.), "ETERNACOLL" (registered trademark) OXBP, OXTP (all are trade names, manufactured by Ube Industries, Ltd.), and the like can be given, and each can be obtained from each company.

[0195] As the bismaleimide compounds, for example, 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane can be given.

[0196] As the isocyanate compounds, for example, 4,4'-methylenebis(phenyl isocyanate) (MDI), toluene diisocyanate (TDI), and the like aromatic polyisocyanates; hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-butanediisocyanate, pentamethylene diisocyanate, lysine diisocyanate, and the like aliphatic polyisocyanates; isophorone diisocyanate (IPDI), 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI), and the like alicyclic polyisocyanates, and the like can be given.

[0197] As the blocked isocyanate compounds, compounds obtained by blocking the aforementioned isocyanate compounds with blocking agents such as oxime, lactam, and pyrazole can be given, and the crosslinking temperature can be easily adjusted. The content of the thermal crosslinking agent is preferably 1 to 30% by mass with respect to the total amount of the photosensitive resin composition excluding organic solvents and water.

[0198] <Photosensitive resin composition: organic solvent>

[0199] The photosensitive resin composition used for forming the pixel division layer of the present application preferably contains an organic solvent. Thereby, it is possible to produce in a varnish state, and it is possible to improve the coatability.

[0200] The aforementioned organic solvent can be used alone or in combination with a polar aprotic organic solvent such as γ-butyrolactone, an ether 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, a ketone such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, an ester such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, 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, an aromatic hydrocarbon such as toluene, xylene, an amide such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

[0201] The amount of the aforementioned organic solvent used is not particularly limited, and is preferably 100 to 3000 parts by mass, and further preferably 150 to 2000 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the organic solvent and water. In addition, the proportion of the organic solvent having a boiling point of 180°C or higher relative to the total amount of the organic solvent is preferably 20% by mass or less, and further preferably 10% by mass or less. By making the proportion of the organic solvent having a boiling point of 180°C or higher 20% by mass or less, the amount of gas emitted from the cured product can be suppressed to a low level, and as a result, the reliability of the organic EL device can be improved.

[0202] <Photosensitive resin composition: adhesion improver>

[0203] The photosensitive resin composition for forming the pixel division layer of the present application can contain an adhesion improver. As the adhesion improver, silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, compounds obtained by reacting an aromatic amine compound with a silane compound containing an alkoxy group, and the like can be mentioned. Two or more of them can be contained. By containing these adhesion improvers, the adhesion to a substrate such as a silicon wafer, ITO, SiO2, silicon nitride, and the like can be improved in the case where the photosensitive resin film is developed, and the like. In addition, the resistance to oxygen plasma, UV ozone treatment, and the like used for cleaning and the like can be improved. The content of the adhesion improver is preferably 0.1 to 10% by mass with respect to the total amount of the photosensitive resin composition excluding organic solvents and water.

[0204] <Photosensitive resin composition: surfactant>

[0205] The photosensitive resin composition for forming the pixel division layer of the present application can contain a surfactant as needed for the purpose of improving the wettability to a substrate. The surfactant can use a commercially available compound, and specifically, as a silicone-based surfactant, the SH series, the SD series, the ST series of Dow Corning Toray Silicone Co., Ltd., the BYK series of BYK Chemie Japan K.K., the KP series of Shin-Etsu Silicone Co., Ltd., the DISFOAM series of NOF Corporation, the TSF series of Toshiba Silicones Co., Ltd., and the like can be mentioned, as a fluorine-based surfactant, the "MEGAFACE (registered trademark)" series of Dainippon Ink and Chemicals, Incorporated, the Fluorad series of Sumitomo 3M Ltd., the "Surflon (registered trademark)" series, the "Asahi Guard (registered trademark)" series of Asahi Glass Company, Limited, the EF series of Shinnippon Rika Co., Ltd., the PolyFox series of OMNOVA Solutions Inc., and the like can be mentioned, as a surfactant formed of a polymer of an acrylic and / or methacrylic series, the Polyflow series of Kyoeisha Chemical Co., Ltd., the "DISPARLON (registered trademark)" series of Nippon Shokubai Co., Ltd., and the like can be mentioned, but are not limited thereto.

[0206] The content of the surfactant is preferably 0.001 to 1% by mass, relative to the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0207] <Photosensitive resin composition: coloring material>

[0208] The photosensitive resin composition used for forming the pixel division layer of the present application can contain a coloring material as needed. The coloring material refers to an organic pigment, an inorganic pigment, or a dye. The coloring material can preferably be an organic pigment and / or an inorganic pigment.

[0209] As the organic pigment, for example, diketopyrrolopyrrole pigments, azo pigments such as azo, disazo or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine or metal-free phthalocyanine, anthraquinone pigments such as aminoanthraquinone, diaminoanthraquinone, anthrapyrimidine, xanthene, anthrarufin, indathrene, induline, and induline lake, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, perylene pigments, benzofuranone pigments, or organometal complex pigments can be mentioned.

[0210] As the inorganic pigment, for example, titanium oxide, zinc oxide, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, iron oxide black, cadmium red, iron oxide red, molybdate red, molybdate orange, molybdate vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chromium green, victoria green, ultramarine, Prussian blue, cobalt blue, cerulean blue, cobalt silicon blue, cobalt zinc silicon blue, manganese violet, or cobalt violet can be mentioned.

[0211] As the dye, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigo dyes, carbonium dyes, phthalocyanine dyes, methine or polymethine dyes can be mentioned.

[0212] Regarding the content of the coloring agent, from the viewpoint of obtaining the coloring property required for the cured product, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, relative to the total amount of the photosensitive resin composition excluding the organic solvent and water. In addition, from the viewpoint of obtaining good storage stability, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less, relative to the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0213] <Time-of-flight secondary ion mass spectrometry method>

[0214] Here, the time-of-flight secondary ion mass spectrometry method will be described in detail.

[0215] Time-of-flight type secondary ion mass spectrometry is generally referred to as TOF-SIMS (Time-Of-Flight Secondary Ion Mass Spectrometry). TOF-SIMS is an analysis method in which pulsed primary ions are irradiated to the surface of a solid sample in a high vacuum, and secondary ions released from the solid are mass-separated using a velocity distribution corresponding to the mass, in which light ions are high speed and heavy ions are low speed. By measuring this time-of-flight distribution, a mass spectrum of the surface of the sample can be obtained. By using a sputtering ion gun in this TOF-SIMS analysis, TOF-SIMS analysis is performed while sputtering in the depth direction, and a mass spectrum in the depth direction can be obtained.

[0216] The ion intensity in the present application uses the ion intensity obtained by measurement divided by the number of primary ions irradiated in the measurement (also referred to as the dose), and is the intensity of the secondary ions released per one irradiated primary ion. For the ion intensity average (I 75 C4H 12 N + The ion intensity average (I TMA-1 ) is measured in a range of 20 nm or more and 100 nm or less in the direction from the surface of the pixel division layer toward the substrate. 75 C4H 12 N + The ion intensity is the average of the ion intensity in the range. 75 C4H 12 N + The ion intensity average (I

[0217] The measurement conditions in the TOF-SIMS analysis in the present application are shown below. Analysis is preferably performed under the following conditions.

[0218] Etching ion species: Ar-GCIB

[0219] Etching ion acceleration voltage: 10 kV

[0220] Primary ion species: Bi3 2+

[0221] Primary ion valence: 2

[0222] Primary ion acceleration voltage: 30 kV

[0223] Current value of primary ion: 0.1 pA

[0224] Circulation time: 140 μsec

[0225] Number of primary ion irradiations per 1 pulse: 43.7

[0226] (Current value of ion in 1 cycle × cycle time / elementary charge: 1.602 × 10) -19 / 1st ion valence) = (0.1 × 10 -12 ) × (140 × 10 -6 ) / (1.602×10 -19 ) / (2) = 43.7

[0227] Cumulative number of measurements per measurement point: 65536

[0228] Dosage: 2863923.2

[0229] (Number of ion irradiations per pulse) × (Cumulative number of irradiations per measurement point) = 43.7 × 65536 = 2863923.2

[0230] Secondary ion polarity: positive

[0231] Antistatic: Electron beam irradiated from a diffuse electron gun (electron gun)

[0232] 75 C4H 12 N + ion( 13 CC3H 12 N + Mass number: 75

[0233] 31 CF + Mass number of the ion: 31.

[0234] Next, the analysis of the pixel segmentation layer will be explained. The pixel segmentation layer was obtained using time-of-flight secondary ion mass spectrometry. 75 C4H 12 N + Average ionic strength (I TMA-1 (This refers to the detection of particles within a range of 20 nm to 100 nm from the pixel segmentation layer surface towards the substrate using time-of-flight secondary ion mass spectrometry.) 75 C4H 12 N + The average ion intensity essentially means analyzing the surface area of ​​the pixel segmentation layer.

[0235] The pixel segmentation layer was obtained using time-of-flight secondary ion mass spectrometry. 75 C4H 12 N + Average ionic strength (I TMA-2 (This refers to the detection of particles in the range of 101 nm to 300 nm from the pixel segmentation layer surface towards the substrate using time-of-flight secondary ion mass spectrometry.) 75C4H 12 N + The average value of the ion intensity substantially means that the inner layer region of the pixel division layer is analyzed.

[0236] In the case of analyzing the pixel division layer of the organic EL display device, it is preferable to perform TOF-SIMS analysis on the cured product surface portion of a region that is 2 μm or more apart from the pixel opening end portion in the planar direction. There is a possibility that the film thickness of a region that is 2 μm or less apart from the pixel opening end portion in the planar direction becomes 100 nm or less, and in this case, there is a possibility that mass spectrometry information of a lower layer component other than the pixel division layer is mixed in.

[0237] The information in the direction from the surface of the cured product toward the inside obtained by TOF-SIMS analysis can generally be obtained by converting the sputtering time into the distance in the direction of the inside from the surface of the object. As a method of converting the sputtering time into the distance in the direction of the inside from the surface of the object, for example, there are the following methods: a method of converting the time into the distance according to the relationship between the film thickness of the pixel division layer determined in advance and the sputtering time from the surface of the cured product to the inside of the cured product; or a method of interrupting the acquisition of the profile in the TOF-SIMS analysis, measuring the distance from the surface to the inside of the obtained analysis pit using a stylus-type film thickness gauge, and calculating the sputtering rate in the pixel division layer in advance.

[0238] Note that, for example, in the case of analyzing the pixel division layer of the organic EL display device using the above-described TOF-SIMS, it is necessary to expose the surface of the pixel division layer. Hereinafter, one example of a method of exposing the surface of the cured product will be described, but the exposing method is not limited to the following method.

[0239] As the method of exposing the surface of the pixel division layer, for example, a sputtering gun of argon, cesium, oxygen, gallium, or the like can be used, and thereby the upper portion of the surface of the pixel division layer targeted is removed, and the surface of the pixel division layer is exposed.

[0240] Alternatively, as the exposing method using chemical etching, the surface of the cured product can be exposed by dissolving one or both of the electrodes sandwiched by the pixel division layer using an acid or a base, thereby making a gap between the upper and lower cured products, and peeling the laminate.

[0241] Further, the member of the organic EL display device present at a position more upper than the organic EL layer can be peeled mechanically, and the pixel division layer with the organic EL layer is exposed, and if necessary, the remaining organic EL layer is cleaned using an organic solvent such as tetrahydrofuran, and the obtained substrate is analyzed using the aforementioned method.

[0242] <Fourier Transform Infrared Spectrophotometer (FT-IR)>

[0243] Next, the analysis method for pixel segmentation layers based on Fourier transform infrared spectrophotometer (FT-IR) will be explained.

[0244] FT-IR, or Fourier Transmission-Infrared Spectroscopy, is a method for detecting chemical bonds and lattice vibrations excited by the absorption of infrared light. It is suitable for obtaining qualitative analysis of functional groups and information on chemical structure. Measurement modes such as transmission and ATR (Total Reflection Transmission) can be selected depending on the measurement site and sample morphology, without particular limitation. In this invention, the term "maximum" refers to a peak intensity maximum within a specified wavenumber range. Furthermore, from the perspective of accuracy in intensity calculation, the preferred method for calculating peak intensity is as follows: drawing a baseline from one end of the specified wavenumber range to the other, and calculating the peak intensity from the maximum point at the aforementioned maximum wavenumber to the baseline.

[0245] The determination conditions for FT-IR analysis in this invention are shown below. Analysis is preferably performed under the conditions described below.

[0246] Light source: Glover (SiC)

[0247] Detector: DLaTGS

[0248] Resolution: 4cm -1

[0249] Total number of times: 256

[0250] Accessory: Thunderdome single-reflection ATR, incident angle 45°, using a Ge prism.

[0251] <Manufacturing Method of Organic EL Display Devices>

[0252] For one example of the manufacturing method of the organic EL display device of the present invention, a manufacturing process is used... Figure 1 The following explanation will be based on an organic EL display device. First, wiring and TFTs 2 are formed on a substrate 1, which serves as a resin film. As a process, in addition to TFT formation processes such as "gate electrode formation process", "gate insulating film formation process", "Si film formation process", and "source electrode and drain electrode formation process", wiring for ensuring electrical connection is also provided, which can be formed using all known methods.

[0253] Next, the planarization layer 5 is coated using a spin coating or slot coating method, and then formed and cured by heating. At this time, contact holes are pre-set for connection with the first electrode 7. When the material used for the planarization layer 5 is a photosensitive resin composition, it can be handled by photolithography; when it is non-photosensitive, it can be handled by conventional etching using a resist material as a mask.

[0254] Next, on the planarization layer 5, AgPdCu and ITO are sequentially formed, and patterning processing is performed, thereby manufacturing the first electrode 7.

[0255] Next, a method for manufacturing the pixel division layer 8 will be described by way of example of a method in which a photosensitive resin film formed of a photosensitive resin composition is formed, the photosensitive resin film is subjected to exposure and development, and then subjected to a heating treatment.

[0256] First, on the first electrode 7, a photosensitive resin film formed of a photosensitive resin composition is formed. As a method for forming the photosensitive resin film, for example, a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like can be given. After coating, a reduced pressure drying treatment is performed as necessary. The reduced pressure drying speed is also dependent on the vacuum chamber volume, the vacuum pump capacity, the piping diameter between the chamber and the pump, and the like, but for example, it is preferable to set a condition in which the vacuum chamber is reduced to 40 Pa after 60 seconds elapses in a state in which the coated substrate is not present.

[0257] After coating or after reduced pressure drying, the coated film is generally subjected to a heating drying. This step is also referred to as a pre-baking. The drying uses a hot plate, an oven, infrared rays, or the like. In the case of using a hot plate, the coated film is directly held on the plate and heated, or the coated film is held on a jig such as a fixing pin provided on the plate and heated. The heating time is preferably 1 minute to several hours. The heating temperature varies depending on the kind of the coated film and the purpose, but from the viewpoint of promoting the drying of the solvent at the time of pre-baking, it is preferable to be 80°C or higher, and further preferable to be 90°C or higher. On the other hand, from the viewpoint of reducing the curing at the time of pre-baking, it is preferable to be 150°C or lower, and further preferable to be 140°C or lower.

[0258] The photosensitive resin film described above can be patterned. For example, the photosensitive resin film can be exposed by irradiating chemical rays through a photomask having a desired pattern, and a desired pattern can be formed by performing development.

[0259] As the chemical rays used in the exposure, ultraviolet light, visible light, electron beams, X-rays, or the like can be given. In the present application, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. In the case of having a positive photosensitivity, the exposed portion is dissolved in a developer.

[0260] After the exposure, in the case of a positive type, the exposed portion is removed using a developer, and thereby a desired pattern is formed. As the developer, tetramethylammonium hydroxide is used. As the development method, a spraying method, a spin immersion method, an immersion method, an ultrasonic method, or the like can be given.

[0261] Next, the pattern formed by development is preferably subjected to a rinsing treatment with distilled water. Instead of distilled water, alcohol such as ethanol or isopropyl alcohol, ester such as ethyl lactate or propylene glycol monomethyl ether acetate, or the like can be added to distilled water to perform the rinsing treatment.

[0262] Next, the developed photosensitive resin film is subjected to a heating treatment, whereby a pixel partition layer is obtained. From the viewpoint of further reducing the amount of outgassing from the cured film, the heating treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, further preferably 230°C or higher, and particularly preferably 250°C or higher. On the other hand, from the viewpoint of improving the film toughness of the cured film, it is preferably 500°C or lower, and more preferably 450°C or lower. Within this temperature range, the temperature can be raised in stages or continuously. From the viewpoint of further reducing the amount of outgassing, the heating treatment time is preferably 30 minutes or longer. From the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or shorter. For example, the following methods can be mentioned: a method in which heating treatment is performed at 150°C and 250°C for 30 minutes each; a method in which heating treatment is performed while linearly raising the temperature from room temperature to 300°C over 2 hours; and the like.

[0263] As the atmosphere during the heating treatment, from the viewpoint of improving the long-term reliability of the cured film, and particularly of suppressing a decrease in luminance during high-temperature continuous driving in the case of an organic EL display device, it is preferably under a low oxygen concentration of less than 5%. As a non-reactive gas for making the oxygen concentration less than 5%, nitrogen, argon, or the like can be mentioned. The oxygen concentration in the non-reactive gas atmosphere is preferably less than 5%, more preferably less than 1%, further preferably less than 0.5%, and particularly preferably less than 0.01%.

[0264] Next, each layer of the hole transport layer, the light-emitting layer, the electron transport layer, and the like that constitute the organic EL layer 9 can be formed by a known method, for example, by a vacuum evaporation method or an inkjet method.

[0265] The mask evaporation method, which is one of the vacuum evaporation methods, is a method of evaporating an organic compound using an evaporation mask to perform patterning, and for example, a method in which an evaporation mask having an opening portion in a desired pattern is disposed on the substrate on the evaporation source side to perform evaporation can be mentioned. In order to obtain a high-precision evaporation pattern, it is important to adhere the evaporation mask having high planarity to the substrate, and a technique of applying tension to the evaporation mask, a technique of adhering the evaporation mask to the substrate using a magnet disposed on the back surface of the substrate, or the like can be generally employed. As a method of manufacturing the evaporation mask, etching, mechanical polishing, a sandblasting method, a sintering method, a laser processing method, use of a photosensitive resin, an electroforming method, or the like can be mentioned, but in the case where a fine pattern is required, an etching method or an electroforming method, which are excellent in processing precision, is preferably employed.

[0266] In the organic EL display device of the present application, a second electrode 10 is also formed. The method of formation can use a known method, but in order to easily avoid deterioration or damage of the organic EL layer 9 which becomes the substrate, a vacuum evaporation method is preferred.

[0267] <Method for producing photosensitive resin composition>

[0268] The photosensitive resin composition used in the production of the pixel division layer of the present application can be obtained, for example, by dissolving an alkali-soluble resin, a quinonediazide compound, and, as needed, an organic solvent, a thermal crosslinking agent, a thermal acid generator, an adhesion improver, a surfactant, a coloring material, inorganic particles, and the like.

[0269] As the method of dissolution, agitation and heating can be mentioned. In the case of heating, the heating temperature is preferably set within a range that does not impair the properties of the photosensitive resin composition, and is usually room temperature to 80°C. In addition, the order of dissolution of the components is not particularly limited, and for example, a method in which the compounds with low solubility are dissolved first can be mentioned. In addition, for components such as surfactants and some adhesion improvers, which are prone to generate bubbles when dissolved by agitation, the other components can be dissolved and then added last, thereby preventing poor dissolution of the other components due to the generation of bubbles.

[0270] The obtained photosensitive resin composition is preferably filtered using a filter to remove dirt and particles. The filter pore size is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm, or the like, but is not limited thereto. The material of the filter is, for example, polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), or the like, and polyethylene and nylon are preferred.

[0271] Example

[0272] Hereinafter, the present application will be described by citing examples, but the present application is not limited by these examples. Note that the evaluation of the photosensitive resin composition in the examples is performed by the following methods.

[0273] (1) TOF-SIMS analysis

[0274] <Production of pixel division layer>

[0275] Figure 2A schematic diagram of the substrate used is shown in FIG. 1. First, on an alkali-free glass substrate 11 of 38 x 46 mm, an ITO transparent conductive film 100 nm was formed on the entire surface of the substrate by a sputtering method, and etched as a first electrode 12. Also, at the same time, an auxiliary electrode 13 was formed for the purpose of taking out the second electrode. The obtained substrate was subjected to ultrasonic cleaning for 10 minutes using "Semico Clean 56" (trade name, manufactured by Furuuchi Chemical Co., Ltd.), and then cleaned using ultrapure water. Next, on the entire surface of the substrate, a photosensitive resin composition according to each of the examples and comparative examples described below was applied by a spin coating method, and prebaked on a hot plate at 120°C for 2 minutes. With respect to the film, UV exposure was performed through a photomask using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.) with an ultrahigh pressure mercury lamp as a light source (mixed line of g line, h line, and i line), and then developed using a 2.38 mass% TMAH aqueous solution, and only the exposed portion was dissolved, and then rinsed using pure water. With respect to the obtained substrate with a pattern, using an inert oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.), curing was performed in an oven under a nitrogen atmosphere at the temperature described in each of the examples and comparative examples for 60 minutes. By the operation described above, a pixel division layer 14 having a shape in which each of the opening portions of 50 μm in width and 260 μm in length exposed the first electrode was defined in the effective area of the substrate, with the opening portions arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction. By the operation described above, a pixel division layer having an opening ratio of 18% was provided in the effective area of the substrate in the shape of a quadrangle with one side of 16 mm, and the thickness of the pixel division layer was about 2.0 μm. Further, with respect to the examples and comparative examples in Tables 1 and 2 in which "yes" is described in the row of "acid cleaning", the pixel division layer after curing was immersed in each of the acidic aqueous solutions for 2 minutes or 10 minutes, and then rinsed using distilled water, and acid cleaning was performed. In the acid cleaning, carbonic acid (weak acid) and hydrochloric acid (strong acid) were used, and acidic aqueous solutions adjusted so that the respective pHs were 4.7 and 1.0 were used.

[0276] <Positive secondary ion detection based on TOF-SIMS depth direction analysis>

[0277] With respect to the pixel division layer portion of the obtained substrate with a pixel division layer, TOF-SIMS depth direction analysis was performed using the following device, and the secondary ions generated at the time of TOF-SIMS depth direction analysis were measured.

[0278] Device: TOF.SIMS5 (manufactured by ION-TOF)

[0279] Etching ion species: Ar-GCIB

[0280] Etching ion acceleration voltage: 10kV

[0281] Primary ion type: Bi3 2+

[0282] Primary ion valence: 2

[0283] First ion acceleration voltage: 30kV

[0284] Primary ion current: 0.1 pA

[0285] Cycle time: 140 μs

[0286] Number of ion irradiations per pulse: 43.7

[0287] (Current value of ion in 1 cycle × cycle time / elementary charge: 1.602 × 10) -19 / 1st ion valence) = (0.1 × 10 -12 ) × (140 × 10 -6 ) / (1.602×10 -19 ) / (2) = 43.7

[0288] Cumulative number of measurements per measurement point: 65536

[0289] Dosage: 2863923.2

[0290] (Number of ion irradiations per pulse) × (Cumulative number of irradiations per measurement point) = 43.7 × 65536 = 2863923.2

[0291] Secondary ion polarity: positive

[0292] Antistatic: Electron beam irradiated from a diffuse electron gun (electron gun)

[0293] 75 C4H 12 N + ion( 13 CC3H 12 N + Mass number: 75

[0294] 31 CF + Mass number of the ion: 31.

[0295] Calculate the results obtained in this analysis 75 C4H 12 N +The value of the ion intensity is obtained in addition to the value obtained by the aforementioned dose, with respect to a thickness direction range of 20 nm or more and 100 nm or less from the pixel division layer surface toward the substrate direction 75 C4H 12 N + The ion intensity is calculated for the range 75 C4H 12 N + The ion intensity average value (I TMA-1 ).

[0296] Using the measured value of the etching pit depth of the thickness in the present analysis, the etching rate is calculated, and the thickness information is obtained.

[0297] (2) FT-IR analysis

[0298] <Infrared spectrum measurement based on FT-IR and calculation of each index>

[0299] Using FT-IR, the pixel division layer described in the aforementioned (1) TOF-SIMS analysis <Manufacture of pixel division layer> is analyzed.

[0300] Apparatus: FT-IR TENSOR2 (manufactured by Bruker Corporation)

[0301] Light source: Glover (SiC)

[0302] Detector: DLaTGS

[0303] Resolution: 4 cm -1

[0304] Cumulative number: 256 times

[0305] Accessories: Thunderdome single reflection ATR, incident angle 45°, Ge prism used.

[0306] (3) Long-term reliability test

[0307] <Long-term reliability evaluation>

[0308] After performing nitrogen plasma treatment as pretreatment with respect to the substrate described in the aforementioned (1) TOF-SIMS analysis <Manufacture of pixel division layer>, an organic EL layer 15 is formed using a vacuum evaporation method. Note that the degree of vacuum at the time of evaporation is 1 x 10 -3Pa or less, in the vapor deposition, the substrate was rotated with respect to the vapor deposition source. First, 10 nm of the compound (HT-1) was vapor-deposited as a hole injection layer, and 50 nm of the compound (HT-2) was vapor-deposited as a hole transport layer. Next, on the light-emitting layer, the compound (GH-1) as a host material and the compound (GD-1) as a dopant material were vapor-deposited to a thickness of 40 nm so that the doping concentration would be 10%. Next, as an electron transport material, the compound (ET-1) and the compound (LiQ) were 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.

[0309] [Chemical Formula 8]

[0310]

[0311] Next, 2 nm of the compound (LiQ) was vapor-deposited, and then Mg and Ag were vapor-deposited in a volume ratio of 1:10 to a thickness of 60 nm to form the second electrode 16. Finally, the glass cap plate was bonded using an epoxy-based adhesive in a low-humidity nitrogen atmosphere, and thus the sealing was performed, and four light-emitting devices (which were quadrilaterals with one side of 5 mm) were produced on one substrate. Note that the film thickness referred to here is the value displayed in a quartz oscillation film thickness monitor.

[0312] The organic EL display device produced was stored at 100°C in an air atmosphere, and every 100 hours, the organic EL display device was taken out, and light emission was performed by direct current driving at 10 mA / cm2, and the light emission area in the light emission pixel was measured. When the initial light emission area before the reliability test was set to 100, the minimum time until the light emission area after the long-term storage became 50 or less was determined as the long-term reliability (unit: hours), and the case where the minimum time was less than 450 hours was determined as property (E), the case where the minimum time was 450 hours or more and less than 500 hours was determined as property (D), the case where the minimum time was 500 hours or more and less than 550 hours was determined as property (C), the case where the minimum time was 550 or more and less than 600 hours was determined as property (B), the case where the minimum time was 600 hours or more and less than 650 hours was determined as property (A), the case where the minimum time was 650 hours or more and less than 700 hours was determined as property (S), the case where the minimum time was 700 hours or more and less than 750 hours was determined as property (S+), the case where the minimum time was 750 hours or more and less than 800 hours was determined as property (S++), and the case where the minimum time was 800 hours or more was determined as property (S+++).

[0313] (4) Bending reliability test

[0314] < Bending reliability evaluation >

[0315] On the central part of a 100 mm x 100 mm polyimide film Kapton 100H (trade name, manufactured by DU PONT-TORAY CO., LTD.) as a substrate, as a first electrode, AgPdCu (100 nm) and ITO (10 nm) were sequentially formed by a vacuum sputtering method, and etched in a stripe shape of 60 μm in line width, 100 μm in pitch, 10 mm in length, and 100 lines. That is, the exposed part of the substrate was 40 μm wide. The photosensitive resin composition according to each of the examples and comparative examples was applied by a spin coating method, and then, pre-baked on a hot plate at 120°C for 2 minutes to form a film.

[0316] After UV exposure of the film through a photomask in a stripe pattern, development was performed using a 2.38 mass% TMAH aqueous solution, and only the exposed part was dissolved, and then, rinsing was performed using pure water to obtain a pattern. Then, curing was performed in an oven at 250°C under a nitrogen atmosphere for 60 minutes to obtain a substrate having a pattern of a pixel division layer. Note that the film thickness of the pixel division layer was adjusted by adjusting the rotation speed in the spin coating method, and thus, the film thickness of the pixel division layer was 1.5 μm in all of the examples and comparative examples.

[0317] On the obtained substrate having a pattern of a pixel division layer, an organic EL layer was formed in the same configuration as the method described in the aforementioned <Reliability Evaluation>. Further, Mg and Ag were evaporated in a volume ratio of 10:1 in a stripe shape of 400 μm in line width, 500 μm in pitch, 10 mm in length, and 20 lines, as a second electrode, in a manner crossing the first electrode. Note that the film thickness referred to here is a displayed value of a quartz oscillation film thickness monitor. The organic EL display device having 100 lines of the first electrode, 20 lines of the second electrode, and 200 light emitting elements where they cross was completed by the operation as described above. A schematic diagram of the organic EL display device of the present example is shown in FIG. 1. Figure 3 .

[0318] As Figure 4As shown, a metal cylinder having a diameter of 5 mm was fixed to the center of the surface of the substrate (100 mm x 100 mm) on which the light emitting element was not formed, and a bending operation was repeated along the cylinder from a winding angle of 0° of the cylinder (a state in which the substrate was flat) to a winding angle of 180° of the cylinder (a state in which the substrate was folded on the cylinder). After the bending operation, the bent portion was observed using an optical microscope. When peeling of the organic EL layer from the substrate occurred, the bending reliability was low in the case where the bending operation was performed 1 to 49 times, and the characteristics were determined to be (E). The case where the bending operation was performed 50 to 99 times was determined to be characteristics (D), the case where the bending operation was performed 100 to 499 times was determined to be characteristics (C), the case where the bending operation was performed 500 to 999 times was determined to be characteristics (B), and the case where the bending operation was performed 1,000 times or more was determined to be characteristics (A) because the bending reliability was high. Note that the test was performed 10 times (n = 10), and the result in which peeling occurred the least number of times was adopted.

[0319] (5) Crack resistance test

[0320] <Crack resistance evaluation>

[0321] A photosensitive resin composition obtained in each of the examples and comparative examples was applied to a polyimide film substrate by spin coating so that the film thickness after heat treatment (curing) was 2.0 μm, and a pre-baking film was produced by pre-baking at 120°C for 120 seconds. Then, without UV exposure, development was performed using a 2.38 mass% TMAH aqueous solution so that the film loss of the unexposed portion was about 0.5 μm. Subsequently, a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. was used to cure at 250°C for 60 minutes under a nitrogen atmosphere, and a cured film was produced.

[0322] Next, the polyimide film substrate provided with the cured film was cut out in 10 pieces with a size of 50 mm long x 10 mm wide. Next, with the surface of the cured film as the outer side, the polyimide film substrate was held for 30 seconds in a state of being bent on a line of 25 mm long in a range of a radius of curvature of 0.1 to 1.0 mm. After 30 seconds, the bent polyimide film substrate was unfolded, and using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), the bent portion on the line of 25 mm long on the surface of the cured film was observed, and the appearance change of the surface of the cured film was evaluated. The bending test was performed in a range of a radius of curvature of 0.1 to 1.0 mm, and the smallest radius of curvature at which no appearance change such as peeling of the cured film from the polyimide film substrate, cracks on the surface of the cured film, and the like occurred was recorded. In the case where the smallest radius of curvature was less than 0.2 mm, it was determined as "A", in the case where the smallest radius of curvature was 0.2 mm or more and less than 0.4 mm, it was determined as "B", in the case where the smallest radius of curvature was 0.4 mm or more and less than 0.6 mm, it was determined as "C", and in the case where the smallest radius of curvature was 0.6 mm or more, it was determined as "D".

[0323] (6) Compounds used in Examples and Comparative Examples

[0324] <Resin>

[0325] Synthesis Example 1 Synthesis of Acid Dianhydride Raw Material

[0326] Under a stream of dry nitrogen, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) 18.3 g (0.05 mol) and propylene oxide 17.4 g (0.3 mol) were dissolved in γ-butyrolactone (hereinafter referred to as GBL) 100 g, and cooled to -15°C. To this, endo-tetracarboxylic anhydride chloride 22.1 g (0.11 mol) which had been dissolved in GBL 50 g was added dropwise in such a manner that the temperature of the reaction liquid did not exceed 0°C. After the dropwise addition was completed, the reaction was carried out at 0°C for 4 hours. The solution was concentrated using a rotary evaporator, and poured into toluene 1 L to obtain an acid dianhydride represented by the following formula.

[0327] [Chemical Formula 9]

[0328]

[0329] Synthesis Example 2 Synthesis of Diamine A

[0330] BAHF 18.3 g (0.05 mole) was dissolved in acetone 100 mL and propylene oxide 17.4 g (0.3 mole) and cooled to -15°C. To this was added dropwise a solution of 3-nitrobenzoyl chloride 20.4 g (0.11 mole) dissolved in acetone 100 mL. After the dropwise addition was completed, the reaction was allowed to proceed for 4 hours at -15°C and then allowed to warm to room temperature. The white solid that precipitated was filtered off and dried under vacuum at 50°C.

[0331] The solid 30 g was charged into a 300 mL stainless steel autoclave, dispersed in methyl cellosolve 250 mL, and 5% palladium-carbon 2 g was added. Hydrogen was introduced into the mixture using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the balloon was no longer deflated, and the reaction was terminated. After the reaction was terminated, the palladium compound that served as the catalyst was removed by filtration, and concentration was carried out using a rotary evaporator to obtain diamine A represented by the following formula.

[0332] [Chemical Formula 10]

[0333]

[0334] Synthesis Example 3 Synthesis of Diamine B

[0335] Into a 500 mL four-necked flask equipped with a stirrer, a thermocouple, and a dropping funnel, BisP-HTG (4,4'-(3,3,5-trimethylcyclohexylidene) bisphenol; manufactured by Hyosung Chemical Co., Ltd.) 26.70 g (0.086 mole) and glacial acetic acid 100 mL were charged, and stirring was carried out, and the internal temperature was raised to 50°C using a hot water bath. Concentrated nitric acid 2 mL (0.026 mole) was added dropwise over a period of 1 hour, and then ice cooling was carried out to lower the internal temperature to 13°C, and further concentrated nitric acid 13.3 mL (0.149 mole) was added dropwise over a period of 1 hour. Then, stirring was continued for 3 hours, and the yellow crystals that precipitated were filtered off, washed sequentially with glacial acetic acid 40 mL and deionized water 80 mL, and dried under reduced pressure to obtain a dinitro compound.

[0336] Next, a four-necked flask having a capacity of 2 L equipped with a stirrer, a thermocouple, a Dimroth condenser, and a dropping funnel was charged with the above-mentioned dinitro compound 54.06 g (0.135 mole), hydrazine monohydrate 180 mL (3.71 mole), and ethanol 900 mL, and stirred under ice cooling. To the mixture was added dropwise 5% palladium-carbon (FUJIFILM Wako Pure Chemical Corporation) 0.9 g suspended in ethanol 30 mL over 1 hour. Then, the solution was subjected to reflux for 2 hours, and the palladium-carbon was removed by filtration while washing with ethanol 300 mL. The entire solvent was removed by heating under reduced pressure, and the residue was washed with ice-cooled ethanol 75 mL, and further washed with deionized water 75 mL and diethyl ether 150 mL in this order, and dried under reduced pressure to obtain diamine B represented by the following formula.

[0337] [Chemical Formula 11]

[0338]

[0339] Synthesis Example 4 Synthesis of diamine C

[0340] The above-mentioned diamine B 17.0 g (0.05 mole) was dissolved in acetone 100 mL and propylene oxide (Tokyo Chemical Industry Co., Ltd.) 17.4 g (0.3 mole), and cooled to -15°C. To the mixture was added dropwise a solution in which 3-nitrobenzoyl chloride (Tokyo Chemical Industry Co., Ltd.) 20.4 g (0.11 mole) was dissolved in acetone 100 mL. After the completion of the dropwise addition, the mixture was stirred at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off, and dried under vacuum at 50°C.

[0341] The obtained solid 30 g was charged into a 300 mL stainless autoclave, dispersed in methyl cellosolve 250 mL, and added with 5% palladium-carbon (FUJIFILM Wako Pure Chemical Corporation) 2.0 g. Hydrogen was introduced into the mixture with a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, the balloon was confirmed not to be deflated, and the reaction was completed. After the completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated with a rotary evaporator to obtain diamine C represented by the following formula.

[0342] [Chemical Formula 12]

[0343]

[0344] Synthesis Example 5 Synthesis of diamine D

[0345] Instead of BisP-HTG (manufactured by Shin-Etsu Chemical Co., Ltd.), BisP-IOTD (4,4'-(2- ethylhexylidene)diphenol; manufactured by Shin-Etsu Chemical Co., Ltd.) 25.66 g (0.086 mole) was used to synthesize the dinitro compound, and the dinitro compound 52.44 g (0.135 mole) was used, and otherwise, the same operation as in Synthesis Example 3 was performed to obtain the diamine D represented by the following formula.

[0346] [Chemical Formula 13]

[0347]

[0348] Synthesis Example 6 Synthesis of diamine E

[0349] Instead of diamine B, diamine D 16.4 g (0.05 mole) was used, and otherwise, the same operation as in Synthesis Example 4 was performed to obtain the diamine E represented by the following formula.

[0350] [Chemical Formula 14]

[0351]

[0352] Synthesis Example 7 Synthesis of polyimide precursor resin (PA1)

[0353] Under a stream of dry nitrogen, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) 62.0 g (0.20 mole) was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 500 g. Diamine A 96.7 g (0.16 mole) obtained in Synthesis Example 2 was added thereto together with NMP 100 g, and a reaction was performed at 20°C for 1 hour and then at 50°C for 2 hours. Next, 3-aminophenol 8.7 g (0.08 mole) as an end-capping agent was added together with NMP 50 g, and a reaction was performed at 50°C for 2 hours. Then, a solution obtained by diluting N,N-dimethylformamide dimethyl acetal 47.7 g (0.40 mole) with NMP 100 g was added dropwise over 10 minutes. After the dropwise addition, stirring was performed at 50°C for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and the solution was poured into water 5 L to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried using a vacuum drier at 80°C for 24 hours to obtain the target polyimide precursor (PA1).

[0354] Synthesis Example 8 Synthesis of polyimide precursor resin (PA2)

[0355] Under a stream of dry nitrogen, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride 31.2 g (0.06 mol) and ODPA 43.4 g (0.14 mol) were dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 500 g. The diamine A obtained in Synthesis Example 2, 96.7 g (0.16 mol) was added together with NMP 100 g, and the reaction was carried out at 20°C for 1 hour and then at 50°C for 2 hours. Next, 3-aminophenol 8.7 g (0.08 mol) as an end-capping agent was added together with NMP 50 g, and the reaction was carried out at 50°C for 2 hours. Then, a solution obtained by diluting N,N-dimethylformamide dimethyl acetal 47.7 g (0.40 mol) with NMP 100 g was added dropwise over 10 minutes. After the dropwise addition, stirring was carried out at 50°C for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and the solution was poured into water 5 L to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried with a vacuum drier at 80°C for 24 hours to obtain the target polyimide precursor (PA2).

[0356] Synthesis Example 9 Synthesis of a polyimide precursor resin (PA3)

[0357] Under a stream of dry nitrogen, the acid dianhydride obtained in Synthesis Example 1, 142.8 g (0.20 mol) was dissolved in NMP 500 g. The diamine A obtained in Synthesis Example 2, 96.7 g (0.16 mol) was added together with NMP 100 g, and the reaction was carried out at 20°C for 1 hour and then at 50°C for 2 hours. Next, 3-aminophenol 8.7 g (0.08 mol) as an end-capping agent was added together with NMP 50 g, and the reaction was carried out at 50°C for 2 hours. Then, a solution obtained by diluting N,N-dimethylformamide dimethyl acetal 47.7 g (0.40 mol) with NMP 100 g was added dropwise over 10 minutes. After the dropwise addition, stirring was carried out at 50°C for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and the solution was poured into water 5 L to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried with a vacuum drier at 80°C for 24 hours to obtain the target polyimide precursor (PA3).

[0358] Synthesis Example 10 Synthesis of a polyimide resin (PA4)

[0359] Under a stream of dry nitrogen, BAHF 124.53 g (0.34 mole) and 1,3-bis(3- aminopropyl)tetramethyldisiloxane 4.97 g (0.02 mole), and 4-aminophenol 8.73 g (0.08 mole) as an end-capping agent were dissolved in NMP 120 g. ODPA 124.09 g (0.4 mole) was added thereto with NMP 40 g, and the reaction was carried out at 20°C for 1 hour, followed by 50°C for 4 hours. Then, xylene 40 g was added, and the solution was stirred at 150°C for 5 hours while water was distilled off together with xylene. After the completion of the stirring, the solution was cooled to room temperature, and the solution was poured into water 10 L to obtain a precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried with a vacuum drier at 80°C for 20 hours to obtain a powder of polyimide resin (PA4).

[0360] Synthesis Example 11 Synthesis of polyimide precursor resin (PA5)

[0361] Under a stream of dry nitrogen, ODPA 62.0 g (0.20 mole) was dissolved in NMP 500 g. The diamine C obtained in Synthesis Example 2, 92.6 g (0.16 mole), was added thereto with NMP 100 g, and the reaction was carried out at 20°C for 1 hour, followed by 50°C for 2 hours. Next, 3-aminophenol 8.7 g (0.08 mole) as an end-capping agent was added thereto with NMP 50 g, and the reaction was carried out at 50°C for 2 hours. Then, a solution obtained by diluting N,N-dimethylformamide dimethyl acetal 47.7 g (0.40 mole) with NMP 100 g was added dropwise over 10 minutes. After the dropwise addition, the solution was stirred at 50°C for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and the solution was poured into water 5 L to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried with a vacuum drier at 80°C for 24 hours to obtain the target polyimide precursor (PA5).

[0362] Synthesis Example 12 Synthesis of polyimide precursor resin (PA6)

[0363] Under a stream of dry nitrogen, ODPA 62.0 g (0.20 mole) was dissolved in NMP 500 g. The diamine E obtained in Synthesis Example 2, 90.7 g (0.16 mole), was added thereto together with NMP 100 g, and the reaction was carried out at 20°C for 1 hour and then at 50°C for 2 hours. Next, 3-aminophenol 8.7 g (0.08 mole) as an end-capping agent was added together with NMP 50 g, and the reaction was carried out at 50°C for 2 hours. Then, a solution obtained by diluting N,N-dimethylformamide dimethyl acetal 47.7 g (0.40 mole) with NMP 100 g was added dropwise over 10 minutes. After the dropwise addition, stirring was carried out at 50°C for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and the solution was poured into water 5 L to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried with a vacuum drier at 80°C for 24 hours to obtain the target polyimide precursor (PA6).

[0364] Synthesis Example 13 Synthesis of polybenzoxazole precursor resin (PB1)

[0365] Under a stream of dry nitrogen, a mixture of dicarboxylic acid derivatives obtained by reacting diphenyl ether-4,4'-dicarboxylic acid 46.5 g (0.18 mole) and 1-hydroxy-1,2,3-benzotriazole 48.6 g (0.36 mole), 0.18 mole, and BAHF 73.3 g (0.20 mole) were dissolved in NMP 570 g, and the reaction was carried out at 75°C for 12 hours. Next, 5-norbornene-2,3-dicarboxylic anhydride 6.6 g (0.04 mole) dissolved in NMP 70 g was added, and stirring was further carried out for 12 hours to complete the reaction. The reaction mixture was filtered, and the reaction mixture was poured into a solution of water / methanol = 3 / 1 (volume ratio) to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried with a vacuum drier at 80°C for 24 hours to obtain the target polybenzoxazole precursor (PB1).

[0366] Synthesis Example 14 Synthesis of polybenzoxazole precursor resin (PB2)

[0367] A mixture of dicarboxylic acid derivative obtained by reacting diphenyl ether-4,4'-dicarboxylic acid 46.5 g (0.18 mole) with 1-hydroxy-1,2,3-benzotriazole 48.6 g (0.36 mole) under a stream of dry nitrogen 0.18 mole and diamine B 68.1 g (0.20 mole) was dissolved in NMP 570 g, and then the reaction was carried out at 75°C for 12 hours. Next, 5-norbornene-2,3-dicarboxylic acid anhydride 6.6 g (0.04 mole) dissolved in NMP 70 g was added, and further stirring was carried out for 12 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was put into a water / methanol = 3 / 1 (volume ratio) solution to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried with a vacuum drier at 80°C for 24 hours to obtain the target polybenzoxazole precursor (PB2).

[0368] Synthesis Example 15 Synthesis of polyhydroxystyrene (PC1)

[0369] To a mixture obtained by adding sec-butyl lithium 2.56 g (0.04 mole) as an initiator to tetrahydrofuran 2400 g was added p-tert-butoxystyrene 105.75 g (0.6 mole), and polymerization was carried out while stirring for 3 hours, and then methanol 12.82 g (0.4 mole) was added to carry out a polymerization termination reaction. Next, to purify the polymer, the reaction mixture was put into methanol 3 L, and the polymer that had settled was dried. The obtained polymer was dissolved in acetone 1.6 L, and concentrated hydrochloric acid 2 g was added at 60°C, and stirring was carried out for 7 hours to deprotect p-tert-butoxystyrene and convert it to hydroxystyrene. After the reaction was completed, the solution was put into water, and the polymer was precipitated. The obtained precipitate was washed with water 3 times, and dried with a vacuum drier at 50°C for 24 hours to obtain the target polyhydroxystyrene (PC1).

[0370] <Quinonediazide compound>

[0371] Synthesis Example 16 Synthesis of quinonediazide compound (Q1)

[0372] TrisP-PA (trade name, manufactured by Hokuriku Chemical Industry Co., Ltd.) 21.22 g (0.05 mole) and diazonaphthoquinone-5-sulfonyl chloride 36.27 g (0.135 mole) were dissolved in 1,4-dioxane 450 g under a stream of dry nitrogen, and allowed to stand at room temperature. To this was added triethylamine 15.18 g, which had been mixed with 1,4-dioxane 50 g, dropwise in such a manner that the system did not become 35°C or higher. After the dropwise addition, stirring was carried out at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was put into water. Then, the precipitate that had separated was collected by filtration. The precipitate was dried with a vacuum drier to obtain a quinonediazide compound (Q1) represented by the following formula.

[0373] [Chemical Formula 15]

[0374]

[0375] <Heat acid generator>

[0376] • T1: Di-p-toluene sulfonic acid 1,3-propanediyl ester (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0377] <Heat crosslinking agent>

[0378] • HMOM-TPHAP (compound represented by the following chemical formula, manufactured by Hokuriku Chemical Industry Co., Ltd.)

[0379] [Chemical Formula 16]

[0380]

[0381] <Organic solvent>

[0382] • PGME: Propylene glycol monomethyl ether

[0383] • GBL: γ-Butyrolactone.

[0384] Example 1

[0385] Under a yellow lamp, PA1 5.4 g obtained in Synthesis Example 3, PB1 4.6 g obtained in Synthesis Example 13, PC1 1.7 g obtained in Synthesis Example 15, Q1 3.4 g obtained in Synthesis Example 16 as a quinonediazide compound, HMOM-TPHAP 2.0 g as a heat crosslinking agent, and T1 0.3 g as a heat acid generator were weighed, and dissolved in PGME 40.0 g and GBL 10.0 g. Then, the obtained solution was filtered using a filter having a pore size of 1 μm, to obtain a photosensitive resin composition A. Using the obtained photosensitive resin composition, the evaluations of (1) to (5) described above were performed.

[0386] Examples 2 to 20, Comparative Examples 1 to 5

[0387] Using the same method as in Example 1, the photosensitive resin compositions B to T, and photosensitive resin compositions a to d were obtained using the compounds in the kinds and amounts described in Tables 1 and 2. Using the obtained photosensitive resin compositions, the evaluations of (1) to (5) described above were performed.

[0388] In addition, with respect to the photosensitive resin composition A used in Example 1, a calculation method of the molar amount of the imide structure contained in 1 g of the entirety of the components constituting the photosensitive resin composition other than the solvent was shown.

[0389] • Polyimide (PA1): 5.4g

[0390] The amount of imide precursor structure in polyimide PA1: (molar amount of acid dianhydride: 0.20 mol × 2) / (weight of polyimide precursor component: 167.4 g) = 2.4 mmol / g

[0391] • Polybenzoxazole (PB1): 4.6g

[0392] Amount of imide precursor structure: (molar amount of acid anhydride: 0.04 mol) / (weight of polybenzoxazole precursor component: 119.5 g) = 0.3 mmol / g

[0393] • Resin containing phenolic hydroxyl groups (PC1): 1.7g

[0394] Total amount of ingredients other than solvent: 5.7g

[0395] The molar amounts of imide structures and benzoxazole structures contained in 1g of the components constituting photosensitive resin composition A, excluding the solvent, calculated using the above values, are as follows.

[0396] Molar amount of imide structure: 0.8 mmol / g.

[0397] The composition and evaluation results of the examples and comparative examples, as well as the molar amounts of the imide structures of each photosensitive resin composition, are shown in Tables 1 and 2.

[0398] [Table 1]

[0399]

[0400] [Table 2]

[0401]

[0402] As a result, an organic EL display device comprising a substrate having a first electrode, a pixel segmentation layer, an organic EL layer, and a second electrode on a substrate, and satisfying the requirement of detection by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel segmentation layer toward the substrate. 75 C4H 12 N + Average ionic strength (I TMA-1 The value is 10.2 × 10 -4 Below 1.0×10 -4 Compared with Comparative Examples 1 to 5, which do not meet the above conditions, Examples 1 to 20 exhibit extremely good long-term reliability or bending reliability.

[0403] Reference Signs

[0404] 1: substrate

[0405] 2: TFT

[0406] 3: TFT insulating layer

[0407] 4: wiring

[0408] 5: planarization layer

[0409] 6: contact hole

[0410] 7: first electrode

[0411] 8: pixel dividing layer

[0412] 9: organic EL layer

[0413] 10: second electrode

[0414] 11: alkali-free glass substrate

[0415] 12: first electrode

[0416] 13: auxiliary electrode

[0417] 14: pixel dividing layer

[0418] 15: organic EL layer

[0419] 16: second electrode

[0420] 17: cylinder

[0421] 18: organic EL display device

Claims

1. An organic EL display device comprising a substrate having a first electrode, a pixel dividing layer, an organic EL layer, and a second electrode on a substrate, wherein the detection is performed using time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel dividing layer toward the substrate. 75 C4H 12 N + Average ionic strength (I TMA-1 The value is 10.2 × 10 -4 Below 1.0×10 -4 above.

2. The organic EL display device as claimed in claim 1, wherein, Detection was performed using time-of-flight secondary ion mass spectrometry in the range of 101 nm to 300 nm from the surface of the pixel segmentation layer towards the substrate. 75 C4H 12 N + Average ionic strength (I TMA-2 ) is 5.0 × 10 -4 the following.

3. The organic EL display device as described in claim 1 or 2, wherein, Detection was performed using time-of-flight secondary ion mass spectrometry in the range of 20 nm to 300 nm from the surface of the pixel segmentation layer towards the substrate. 31 CF + Average ionic strength (I CF ) is 0.5×10 -4 the following.

4. The organic EL display device as described in claim 1 or 2, wherein, The pixel segmentation layer contains polyimide and / or polybenzoxazole, the polyimide and / or polybenzoxazole having the structure shown in formula (1). [Chemical Formula 1] In equation (1), X 1 R represents a non-cyclic divalent hydrocarbon group with 4 to 10 carbon atoms. 1 Each of the groups independently represents a hydrocarbon group or hydroxyl group with 1 to 4 carbon atoms, and each of the groups a independently represents an integer from 0 to 4.

5. The organic EL display device as claimed in claim 4, wherein, X in equation (1) 1 The structure shown in equation (2) is as follows. [Chemical Formula 2] In equation (2), R 2 and R 3 Each can independently represent a non-cyclic hydrocarbon group or hydrogen atom with 1 to 9 carbon atoms. This indicates the bonding site that binds to the aromatic ring; it should be noted that R 2 and R 3 The total number of carbon atoms is 3 to 9.

6. The organic EL display device as claimed in claim 1 or 2, wherein, The pixel segmentation layer, in the infrared spectrophotometer measured using a Fourier transform infrared spectrophotometer (FT-IR), at 1365 cm⁻¹ -1 Above 1385cm -1 The index A, which is maximal within the range below 0.10 and 1.10, indicates the presence of imide structures in the pixel segmentation layer. Index A = (1365cm) -1 Above 1385cm -1 (the maximum value below) / (1590cm) -1 The above 1610cm -1 (The following are the maximum values) Among them, the maximum value used in index A above is the intensity value at the absorption maximum measured by FT-IR.

7. The organic EL display device as claimed in claim 1 or 2, wherein, The pixel segmentation layer, in the infrared spectrophotometer determined using FT-IR, at 1040 cm⁻¹ -1 Above 1060cm -1 The index B for the presence of benzoxazole structures is 0.20 to 2.50 relative to the amount of imide structures contained in the pixel segmentation layer. Index B = (1040cm) -1 Above 1060cm -1 (the maximum value below) / (1365cm) -1 Above 1385cm -1 (The following are the maximum values) Among them, the maximum value used in index B above is the intensity value at the absorption maximum measured by FT-IR.

8. The organic EL display device as claimed in claim 1 or 2, wherein, The pixel segmentation layer also contains compounds derived from thermally generated acid agents.

9. The organic EL display device as claimed in claim 1 or 2, wherein, The pixel segmentation layer also contains compounds derived from resins containing phenolic hydroxyl groups.

10. The organic EL display device as claimed in claim 9, wherein, The resin containing phenolic hydroxyl groups is polyhydroxystyrene or a polyhydroxystyrene / polystyrene copolymer.

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