KR20230162926A - Organic EL display device and method of manufacturing the same - Google Patents

Abstract

To provide an organic EL display device that manufactures an organic EL display device including the formation of a pixel division layer and a spacer by a simple method, is highly reliable as a flexible display device, and can suppress external light reflection, and a method for manufacturing the same. The purpose is to The solution is an organic EL display device having a substrate having a first electrode, a pixel split layer, and a spacer on a substrate, and also an organic EL layer and a second electrode, wherein the surface roughness (Ra1) of the pixel split layer and the surface of the spacer are When the maximum value of roughness (Ra2) is taken as Ramax, it is an organic EL display device in which Ramax is 1.0 nm or more and 50 nm or less.

Description

Organic EL display device and method of manufacturing the same

The present invention relates to an organic EL display device having a plurality of display pixels formed in a matrix and a method of manufacturing the same.

Organic EL displays are attracting attention as next-generation flat panel displays. Organic EL is electroluminescence from an organic EL layer made of organic compounds formed between two electrodes. And, a display device using organic EL light-emitting elements is an organic EL display device. Self-luminous organic EL display devices are capable of wide viewing angles, high-speed response, and high-contrast image display, and are being actively researched and developed recently in that they can be made thinner, lighter, and more flexible by using substrates such as thin glass or plastic resin. It is done. Flexible organic EL display devices are expected to be applied in various fields, such as bendable devices that can be bent without cracking, rollable devices that can be rounded, and foldable devices that can be folded.

However, in such a flexible organic EL display device, there is a risk of separation of the substrate and the organic EL layer due to the manufacturing process or usage method such as bending or folding, and as a result, the reliability of the organic EL display device decreases (e.g. For example, see Patent Document 1).

On the other hand, speaking of mobile devices, it is necessary for display devices to maintain display quality in various environments, both indoors and outdoors. In particular, in order to suppress reflection of external light, there are suggestions such as combination with a circular light plate or blackening the substrate (for example, For example, see Patent Document 2).

Japanese Patent Publication No. 2020-87935 Japanese Patent Publication No. 2004-281365

However, in the organic EL display device described in Patent Document 1, in which an inversely tapered spacer is provided on the pixel division layer for the purpose of suppressing peeling for flexibility, the material and manufacturing conditions can be set based on the characteristics of the spacer shape. This was difficult, and there were problems such as the inability to process the pixel division layer and spacer simultaneously, leading to a decrease in the panel product ratio and a significant cost increase.

Additionally, in the organic EL display device described in Patent Document 2 in which the first electrode and the pixel division layer are blackened for the purpose of suppressing external light reflection, suppression of external light reflection by coloring can be expected to some extent, but the smoothness of the reflective surface Suppression of extraneous light reflection from was not sufficient.

Therefore, the present invention provides an organic EL display device that manufactures an organic EL display device including the formation of a pixel split layer and a spacer in a simple manner, is highly reliable as a flexible display device, and can suppress external light reflection, and the same. The purpose is to provide a manufacturing method.

The organic EL display device of the present invention is an organic EL display device having a substrate having a first electrode, a pixel split layer, and a spacer on a substrate, and also an organic EL layer and a second electrode, wherein the surface roughness (Ra1) of the pixel split layer is When Ramax is the maximum value of the surface roughness (Ra2) of the spacer, Ramax is 1.0 nm or more and 50 nm or less.

In addition, the method of manufacturing an organic EL display device of the present invention is a method of manufacturing an organic EL display device having a substrate having a first electrode, a pixel division layer, and a spacer on a substrate, and also an organic EL layer and a second electrode, wherein the pixel division is It has a process for batch processing the layer and the spacer, and the photomask for batch processing is a halftone photomask having a light transmitting part, a light blocking part, and a semi-transmissive part.

In the organic EL display device of the present invention, the production of an organic EL display device including the formation of a pixel dividing layer and a spacer is performed in a simple manner, there is no peeling of the organic EL layer, and external light reflection is suppressed by increasing the diffused reflected light of the substrate. can do.

1 is a schematic cross-sectional view of an organic EL display device in the present invention.
Figure 2 is a schematic cross-sectional view of a substrate as an example of the present invention.
Figure 3 is a schematic cross-sectional view of Ra1 and Ra2 in the present invention.
Figure 4 is a schematic diagram of the taper angle of the pixel division layer in the present invention.
Figure 5 is a schematic cross-sectional view of a typical organic EL display device.
Figure 6 is a schematic diagram of a first electrode and a halftone photomask according to an embodiment of the present invention.
Figure 7 is a schematic diagram of a bending test according to an embodiment of the present invention.
Figure 8 is a schematic diagram of an organic EL display device according to an embodiment of the present invention.
Figure 9 is a schematic diagram of a light emitting device in an embodiment of the present invention.

Hereinafter, modes for carrying out the present invention (hereinafter referred to as “embodiments”) will be described in detail. Additionally, the present invention is not limited only to the embodiments described below.

<Organic EL display device>

The organic EL display device of the present invention is an organic EL display device having a plurality of display pixels formed in a matrix. Depending on the direction in which light emission from the organic EL layer is extracted, it is broadly classified into top emission and bottom emission, but is not particularly limited. In addition, depending on the driving method, it is roughly divided into a passive driving type in which the electrodes are divided into columns and rows and only the display pixels sandwiched between the electrodes emit light, and an active driving type in which several TFTs are formed in each display pixel and switched. It is not limited.

The organic EL display device of the present invention is an organic EL display device having a substrate having a first electrode, a pixel split layer, and a spacer on a substrate, and also an organic EL layer and a second electrode, wherein the surface roughness (Ra1) of the pixel split layer is and an organic EL display device in which Ramax is 1.0 nm or more and 50 nm or less, when the maximum value of the surface roughness (Ra2) of the spacer is Ramax.

Figure 1 shows a schematic cross-sectional view of an organic EL display device as an example of the present invention. In an organic EL display device, a first electrode (2) is provided on a substrate (1). A pixel is formed in a region on the substrate 1 where the first electrode 2 does not exist (hereinafter, the region on the substrate 1 where the first electrode 2 does not exist may be referred to as a gap of the first electrode). It has a split layer (3) and also has a spacer (4) on the pixel split layer. In an organic EL display device, a unit having a first electrode, a pixel division layer, and a spacer on this substrate is referred to as a substrate. Additionally, by having an organic EL layer 5 and a second electrode 6 on the substrate, it becomes an organic EL display device.

<Substrate>

In the organic EL display device of the present invention, the minimum unit of the substrate is made up of only the base material 1, the first electrode 2, the pixel division layer 3, and the spacer 4, which will be described later. As long as such a minimum unit is provided, the substrate may have a configuration (for example, the configuration shown in FIG. 2) that further includes wiring, a TFT 7, a pattern antenna, and a planarization layer 8. However, in the present invention, everything that forms the basis of the first electrode 2, such as the above-mentioned wiring, TFT 7, sensors, pattern antenna, etc., and the planarization layer 8, is treated as a part of the base material 1. Do it by doing it.

Wiring is often connected to external devices through FPC (Flexible Printed Circuit) for operation. Additionally, in addition to the TFT 7, a camera, sensors such as ID or fingerprint reading or illuminance, and a pattern antenna for communication or power supply may be installed. In this way, in the base material 1 integrating multiple functions, it is preferable to form the planarization layer 8. By forming the planarization layer 8, it is possible to flatten the substrate 1 by covering irregularities such as wiring and the TFT 7 before forming the first electrode 2. By planarizing the substrate 1, defects in the first electrode 2, pixel division layer 3, and spacer 4 formed on the substrate can be prevented, and a high-quality substrate can be obtained. Figure 2 shows a schematic cross-sectional view of a substrate as an example of the present invention.

<Description>

Among the substrate 1 in FIG. 1 and the substrate 1 in FIG. 2, the base 1a of the substrate below the TFT 7 is used for supporting the display device or for post-processing, such as metal, glass, or resin film. One suitable for conveyance can be appropriately selected. In particular, when flexibility is required, a resin film is preferable.

As glass, soda lime glass, alkali-free glass, etc. can be used. The thickness of the glass should be sufficient to maintain mechanical strength. Regarding the material of the glass, alkali-free glass is preferable since it is better to have fewer ions eluted from the glass, but soda lime glass coated with a barrier coat such as SiO ₂ can also be used.

The material of the resin film preferably contains a resin material selected from polybenzoxazole resin, polyamidoimide resin, polyimide resin, polyamide resin, and poly(p-xylylene) resin because of its excellent light transmittance. do. The base material may contain these resin materials individually or may contain them in combination of multiple types.

For example, when forming a base material with a polyimide resin, a solution containing a polyamic acid (including a polyamic acid in which part of the imidized polyamic acid is partially imidized) resin, which is a precursor of the polyimide resin, or a soluble polyimide resin is applied to the support substrate. It can also be formed by firing.

Additionally, since it is known that the above-mentioned light-emitting element is weak to oxygen and moisture, a gas barrier layer may be formed as appropriate as a component of the base material. In particular, in the case of a resin film, a highly reliable display device can be obtained by laminating inorganic thin films. Additionally, the base material may be one on which wiring, TFT 7, planarization layer 8, etc. are formed.

<First electrode>

The first electrode 2 in the present invention must be a light-transmitting electrode in the case of the bottom emission type, and a light-reflective electrode in the case of the top emission type.

If it is a bottom emission type, for example, conductive metal oxides such as transparent tin oxide, indium oxide, indium tin oxide (ITO), or metals such as gold, silver, and chromium, inorganic conductive materials such as copper iodide and copper sulfide, and polythiide. Conductive polymers such as ophene, polypyrrole, and polyaniline can be used, but are not particularly limited.

If it is a top emission type, a material that exhibits high reflectance of visible light above a certain film thickness and low electrical resistance is preferable. In addition, it is necessary to select a material in terms of wet etching, cleaning, storage, and weather resistance in the use environment in the post-process. In particular, Ag or an Ag alloy film mainly containing Ag is useful because it has a high reflectance. The Ag alloy film can be made of AgPdCu or AgTiCu, etc., whose main component is Ag, and it is preferable to laminate these Ag alloy films with an oxide conductive film such as an ITO film or IZO film because it can achieve low contact resistance with the organic EL layer. . Additionally, Al or an Al alloy film containing Al as a main body is also good as a top emission type first electrode. An Al-Ni alloy film containing 0.1 to 2 at% Ni is preferable because it has a high reflectance at the level of pure Al. In addition, a reflective metal film such as molybdenum (Mo) or tungsten (W) can also be used.

The resistance of the first electrode is not limited as long as it can supply enough current for light emission of the light emitting element, but it is preferable to have low resistance from the viewpoint of power consumption of the light emitting element. For example, ITO of 300 Ω/□ or less functions as a device electrode, but since ITO of about 10 Ω/□ is currently available, it is particularly desirable to use a low-resistance product. The thickness of the first electrode can be arbitrarily selected according to characteristics such as transmittance and resistance, but is usually between 100 and 300 nm.

A known method may be used to form the first electrode. For example, after forming a film using a vacuum film forming method such as sputtering, it can be patterned by etching using a photoresist.

<Pixel division layer>

In the organic EL display device of the present invention, the pixel split layer (3) is formed in the gap of the first electrode (2). Display pixels can be divided by forming a pixel division layer in the gap of the first electrode. That is, by patterning the pixel separation layer in the gap of the first electrode, the exposed portion of the first electrode is limited, and only the opening portion of the pixel separation layer functions as a display pixel. In addition, the pixel division layer covers the peripheral edge of the line-shaped or island-shaped first electrode, preventing short circuits that occur at the edge of the first electrode or disconnection of the second electrode, thereby improving the reliability of the display device. You can. Additionally, in the organic EL display device of the present invention, the pixel split layer is formed in places other than the gap of the first electrode as needed.

In the present invention, when Ramax is the maximum value of the surface roughness (Ra1) of the pixel division layer and the surface roughness (Ra2) of the spacer, Ramax is 1.0 nm or more and 50 nm or less. Additionally, it is more preferable that the surface roughness (Ra1) of the pixel dividing layer is Ramax. Additionally, both the surface roughness (Ra1) of the pixel division layer and the surface roughness (Ra2) of the spacer may be Ramax.

In addition, the atomic force microscope (AFM) used to measure surface roughness in the present invention generally performs measurements from vertically above on the substrate of an organic EL display device placed on a horizontal surface, and measures the target ranges of Ra1 and Ra2. is shown in Figure 3. Therefore, in the present invention, “surface roughness of the pixel split layer” refers to the surface roughness of the surface that can be measured by AFM, that is, the surface that is substantially parallel to the substrate, among the surfaces in contact with the organic EL layer of the pixel split layer.

Additionally, since spacers are formed on the pixel division layer, the portion without spacers becomes an interface in contact with the organic EL layer. Conventionally, because the adhesion between the pixel dividing layer and the organic EL layer was poor, peeling easily occurred, which was a major problem, especially for flexible products. In the present invention, the anchor effect can be obtained by setting the surface roughness (Ra1) of the pixel dividing layer to 1.0 nm or more, and adhesion to the organic EL layer is improved by preferably setting it to 5.0 nm or more, more preferably 20 nm or more. It can be improved.

In addition, with respect to the surface roughness (Ra1) of the pixel dividing layer, an anchor effect can be obtained if it is 1.0 nm or more, but for the purpose of suppressing pinholes in the second electrode and defects in the sealing process described later, it is set to 50 nm or less. It is desirable. In addition, when improving adhesion by increasing Ra1, it is effective to ensure that the interface where the pixel division layer and the organic EL layer contact is as large as possible, and Ra1 is larger than the surface roughness Ra2 of the spacer described later, that is, Ra1 In the case of Ramax, it is preferable that the area of the interface between the pixel division layer and the organic EL layer is 50% or more of the area of the interface between the substrate and the organic EL layer. This indicates that the pixel dividing layer is more than 50% of the surface area of the substrate.

Additionally, depending on the shape of the edge of the pixel division layer, it may cause disconnection of the second electrode, so it is preferable to have a gentle forward taper shape. Here, the forward tapered shape refers to the tangent at the interface between the first electrode and the pixel division layer and the tangent at the position of the film thickness of 50% of the maximum thickness of the pixel division layer on the surface of the tapered portion of the pixel division layer. This refers to a state in which the created angle (hereinafter, this angle may be referred to as the taper angle of the pixel division layer) is less than 90°. In the present invention, in order to obtain a highly reliable display device that suppresses disconnection of the second electrode, the taper angle of the pixel dividing layer is preferably less than 60°, and more preferably less than 50°.

Using FIG. 4, the taper angle of the pixel division layer will be explained in detail. In Fig. 4, a first electrode 2 is provided on the base material 1. A pixel split layer (3) is provided in the gap of the first electrode (2), and a spacer (4) is provided on the pixel split layer. The angle formed by the tangent at the interface between the first electrode and the pixel division layer and the tangent at the position (point A) of the film thickness of 50% of the maximum thickness of the pixel division layer on the surface of the tapered portion of the pixel division layer. (B) is defined as the taper angle of the pixel division layer.

The pixel split layer is not limited to either a known organic material or an inorganic material, but from the viewpoint of easy adjustment of the surface roughness, it is preferable that the pixel split layer includes a cured film of a photosensitive resin composition containing an alkali-soluble resin. The pixel dividing layer may be a single layer or a multilayer. For example, in the case where the pixel dividing layer is a multilayer, the surface substantially parallel to the substrate to be measured for surface roughness is a cured film of a photosensitive resin composition containing an alkali-soluble resin. desirable.

The photosensitive resin composition preferably contains (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) an organic solvent, and may also contain (D) a coloring material and (E) a liquid-repelling material. By containing (A) alkali-soluble resin and (B) a photosensitive agent in combination as a photosensitive resin composition, pattern processing using photosensitivity becomes possible. Additionally, by containing (C) an organic solvent, it can be made into a varnish and the applicability can be improved in some cases. Additionally, when the photosensitive resin composition contains the coloring material (D), the pixel dividing layer can be blackened. Additionally, (E) by containing a liquid-repellent material, liquid-repellent properties can be imparted to the pixel dividing layer. Due to the difference in exposure sensitivity and dissolution speed of the (D) coloring material or (E) liquid-repellent material and (A) alkali-soluble resin, the surface roughness of the pixel division layer and the spacer varies depending on the process using the halftone mask described later. It is desirable in that it can be made large and the surface roughness of the pixel dividing layer and the spacer can be adjusted respectively. The photosensitive resin composition may further contain other components.

A known method may be used to form the pixel division layer. Among them, the wet coating method is preferable because it can uniformly form a thin film on a large substrate. Examples of wet coating methods include spin coating, slit coating, dip coating, spray coating, and printing.

The thickness of the pixel division layer is usually 0.3 μm to 10 μm, but is not particularly limited as long as it is sufficient to cover the unevenness of the first electrode. In addition, patterning processing is essential for the pixel division layer, and residues from the removed area may be directly connected to defects such as short circuits and black spots. In addition, it is necessary to fabricate a spacer on the pixel split layer to support the structure covering the second electrode in the post-process and to secure the strength of the display device.

<(A) Alkali-soluble resin>

Alkali solubility in the present invention means applying a solution in which the resin is dissolved in γ-butyrolactone (GBL) onto a silicon wafer and prebaking it at 120°C for 4 minutes to form a prebaked film with a film thickness of 10 μm ± 0.5 μm. After forming, the prebaked film was immersed in a 2.38% by weight tetramethylammonium hydroxide aqueous solution at 23°C ± 1°C for 1 minute, and then rinsed with pure water, the dissolution rate obtained from the decrease in film thickness was 50 nm/min. It says something more than that.

(A) The alkali-soluble resin preferably has an aromatic carboxylic acid structure from the viewpoint of improving heat resistance. In addition, in the present invention, the aromatic carboxylic acid structure refers to a carboxylic acid structure directly covalently bonded to an aromatic ring.

(A) The alkali-soluble resin is one selected from the group consisting of acrylic resin, phenol resin, polysiloxane resin, Cardo resin, polyimide resin, polyimide precursor resin, polybenzoxazole resin, and polybenzoxazole precursor resin. It is preferable to contain the above.

Among these resins, since heat resistance and chemical resistance are compatible, (A) the alkali-soluble resin contains polyimide resin, polyimide precursor resin, polybenzoxazole resin, and/or polybenzoxazole precursor resin. desirable. High chemical resistance is preferable because film reduction when processing the pixel division layer by wet etching is reduced. Moreover, polyimide precursor resin is particularly preferable because the amount of outgassing under high temperature conditions is small. Additionally, from the viewpoint of improved alkali solubility, a polyimide precursor resin having an amic acid structure is more preferable.

<Silica particles in the pixel division layer>

The pixel split layer in the organic EL display device of the present invention preferably contains (a) silica particles with a primary particle diameter of 5 to 30 nm (hereinafter sometimes referred to as (a) component). It is more preferable that the pixel dividing layer further contains the (D) coloring material described later in addition to the component (a), and in this case, it is more preferable to contain the organic pigment (D1) described later as the (D) coloring material. , (D1) It is more preferable to contain the component (b) described later as the organic pigment. In addition, component (a) preferably has a primary particle diameter of 5 to 30 nm and an aspect ratio (major axis/minor axis) of 1.0 to 1.5. Containing such component (a) has the effect of increasing the uniformity of the opening width of the opening and reducing luminance unevenness. The primary particle diameter here refers to the long diameter of the particle, and silica particles with a primary particle diameter of 5 to 30 nm refer to those with a primary particle diameter within the range of 5 to 30 nm. The "aspect ratio (major axis/minor axis)" herein means the value obtained by dividing the major axis by the minor axis in the primary particle diameter of the silica particle, rounded to the second decimal place.

The silica particles referred to herein include particles with a SiO ₂ content of 90% by weight or more excluding water, particles made of silicon dioxide (anhydrous silicic acid), particles made of silicon dioxide hydrate (hydrous silicic acid), and particles made of quartz glass. It means that The form in which hydrous silicic acid exists is not particularly limited, and particles made of ortho-silicic acid, meta-silicic acid, and/or meta-disilicic acid also correspond to the silica particles referred to herein. Weight excluding water means the weight obtained by subtracting the weight of moisture in the particles from the weight of the particles.

However, in core-shell type composite particles, the surface treatment agent and the coating layer applied as a shell to at least a portion of the surface of the particles that do not contain SiO ₂ as the core, for example, particles made of organic polymers, organic pigments, or inorganic pigments, are Even if SiO ₂ is contained, it is defined that they alone do not correspond to silica particles, regardless of the SiO ₂ content rate. Meanwhile, core-shell composite particles containing SiO ₂ in the core and having a SiO ₂ content of 90% by weight or more excluding water are defined as silica particles. That is, component (a) is filled as particles in a dispersed form in the pixel division layer. The particle structure of component (a) is not particularly limited and may have internal voids.

Silica particles other than the above-described particles made of silicon dioxide, particles made of silicon dioxide hydrate, and particles made of quartz glass include, for example, a composite of silicon and metal with a SiO ₂ content of 90% by weight or more based on the weight excluding water. Examples include silica particles made of oxide. Examples of metals referred to here include zirconium, titanium, and cerium. However, only for silica particles containing hafnium atoms, it is defined as a mixture of silica particles and hafnium atoms (hereinafter sometimes referred to as component (c)).

In further reducing the unevenness of luminance of an organic EL display device, component (a) more preferably contains silica particles with a primary particle diameter of 5 to 20 nm, and contains silica particles with a primary particle diameter of 5 to 15 nm. It is more desirable. The primary particle diameter referred to here refers to the major axis of the silica particle. As for the aspect ratio, it is more preferable to contain silica particles of 1.0 to 1.3, and it is further preferable to contain silica particles of 1.0 to 1.2. Additionally, when the aspect ratio is 1.0, it can be regarded as a spherical silica particle.

Component (a) and silica particles other than component (a) are obtained by thinly cutting the pixel division layer and spacer layer as observation samples, and are preferably subjected to ion milling, more preferably focused ion beam (FIB) processing. For a cross section that was polished and smoothed by pretreatment, a location located in the range of 0.2 to 0.8 ㎛ in the film depth direction from the outermost layer of the pixel division layer or spacer layer was subjected to transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM). By analyzing with -EDX), the elements that make up the particle can be identified and specified from the element mapping information. Transmission electron microscopy-electron energy loss spectroscopy (TEM-EELS) or scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX) can also be used for interpretation.

Specifically, the sample was observed and imaged using a transmission electron microscope-energy dispersive Ltd.), it is possible to distinguish between silica particles corresponding to component (a) and silica particles not corresponding to component (a). That is, in the cross section of the pixel dividing layer, 30 silica particles in the TEM image were randomly selected, and the major axis, minor axis, and aspect ratio of the TEM image were measured for each, and the major axis (nm) was 5 to 30 nm. , and silica particles with an aspect ratio in the range of 1.0 to 1.5 are defined as component (a). Additionally, for one silica particle, if the minor axis and major axis in the TEM image are the same, that is, if it is a perfect circle, the diameter is regarded as the major axis. Representative values representing the characteristics of silica particles corresponding to component (a) are the average value of the primary particle diameter, i.e., the average value of the major axis, calculated and rounded to one decimal place, and the average value of the aspect ratio, i.e. (a) Calculate the average value of the aspect ratio of each silica particle corresponding to the component, and use the value rounded to 2 decimal places. Here, the analysis is performed excluding SiO ₂ having a contact point with the surface of particles such as polymer particles, organic pigments, and/or inorganic pigments. The major axis and aspect ratio of the silica particles contained in the spacer layer can be measured in a similar manner.

In addition, the pixel dividing layer provided in the organic EL display device of the present invention further contains silica particles that do not correspond to component (a), that is, silica particles having a primary particle diameter of less than 5 nm or more than 30 nm, or aspect particles. It may contain silica particles whose ratio (major axis/minor axis) exceeds 1.5. Silica particles that do not correspond to component (a) include, for example, "ADMAFINE" (registered trademark) SO-E2, SO-E4 (all manufactured by ADMATECHS COMPANY LIMITED), KE-P10, KE-S10 (above, Any product made by NIPPON SHOKUBAI CO., LTD. can be mentioned.

The pixel split layer provided in the organic EL display device of the present invention further contains SiO ₂ in a proportion of less than 90% by weight, excluding water, and further contains particles that do not correspond to silica particles in the present specification. Does not matter. As particles that do not correspond to the above-mentioned silica particles, for example, "ATLAS" (registered trademark) 100 (Cabot Corporation), which is an organic-inorganic composite particle with a silica:polymer ratio = weight ratio of 70:30 disclosed in Japanese Patent Application Laid-Open No. 2018-97251. 1) can be mentioned.

The average primary particle diameter of the silica particles contained in the pixel split layer of the organic EL display device of the present invention is preferably 5 to 30 nm, and more preferably 5 to 25 μm, from the viewpoint of suppressing luminance unevenness. The average aspect ratio (major axis/minor axis) is preferably 1.0 to 1.3, and more preferably 1.0 to 1.2. That is, even if the pixel dividing layer of the organic EL display device of the present invention contains silica particles that do not correspond to component (a), the average primary particle diameter of all the silica particles contained is 5 to 30 nm. desirable. Also, similarly, it is preferable that the average aspect ratio (major axis/minor axis) is 1.0 to 1.3. The silica particles referred to herein include both component (a) and silica particles that do not correspond to component (a). The average primary particle diameter referred to here is 0.2 to 0.8 μm in the film depth direction from the outermost layer of the pixel division layer under the condition of a magnification of 50,000 times using the transmission electron microscope-energy dispersive X-ray spectroscopy (TEM-EDX) described above. 1 decimal point of the average value of the major axis of all 30 silica particles obtained at random using an image analysis particle size distribution measuring device (Mac-View, manufactured by MOUNTECH Co., Ltd.) by observing the cross-section located in the range of . This means that the value is rounded off. The “average aspect ratio (major axis/minor axis)” referred to here is the average value obtained by dividing the major axis by the minor axis for each primary particle of all 30 randomly acquired silica particles in the same image, rounded to the second decimal place. It means that it is one value. Silica particles with an average primary particle diameter of 5 to 30 nm mean those with an average primary particle diameter within the range of 5 to 30 nm, and silica particles with an average aspect ratio of 1.0 to 1.3 mean those with an average aspect ratio of 1.0 to 1.3. refers to what is included in the scope of.

The specific surface area of component (a) corresponding to the above-mentioned primary particle diameter is preferably 50 to 500 m2/g, and more preferably 200 to 400 m2/g. The specific surface area referred to here refers to the specific surface area measured by the BET method using nitrogen as the adsorption gas. The surface of the component (a) may be porous or non-porous, and may have an internal surface area.

Examples of the functional group that component (a) has on its surface include a reactive residue of a surface modification group containing an ethylenically unsaturated double bond group, a silanol group, an alkoxysilyl group, a trialkylsilyl group, and a diphenylsilyl group. Among them, in order to further reduce the unevenness of brightness, it is preferable to have a reactive residue of a surface modifying group containing an ethylenically unsaturated double bond group. The reactive residue of the surface modifying group containing an ethylenically unsaturated double bond group as used herein refers to the residue remaining after the ethylenically unsaturated double bond group of the surface modifying group containing an ethylenically unsaturated double bond undergoes radical polymerization reaction by light and/or heat. means that (a) The component contains silica particles having on the surface of the particle a reactive residue of a surface modifying group containing an ethylenically unsaturated double bond group, and the reactive residue of the surface modifying group containing an ethylenically unsaturated double bond group is represented by formula (3) It is more preferable to have a structure represented by and/or a structure represented by formula (4). It is more preferable that the reactive residue of the surface modification group containing the ethylenically unsaturated double bond group is a residue generated by a radical polymerization reaction with a compound having two or more radical polymerizable groups in the molecule, which will be described later.

In formula (3), R ₁₇ ¹⁶ represents a hydrogen atom or a methyl group. R ₁₈ ¹⁷ represents a divalent hydrocarbon group having 1 to 7 carbon atoms. j and k are integers and each independently represents 0 or 1. However, when j is 1, k is 1. * ¹ represents the bonding site with a carbon atom.

* ² represents the bonding site of the silica particle with the oxygen atom bonded to the silicon atom on the particle surface. R ₁₉ ¹⁸ represents an alkyl group having 1 to 3 carbon atoms. m and n are integers, m represents 1 to 3, and n represents 0 to 2. However, m+n=3 is satisfied.

In formula (4), R ₂₀ ¹⁹ represents a hydrogen atom or a methyl group. R ₂₁ ²⁰ represents an oxyalkylene group having 1 to 3 carbon atoms. r is an integer and represents 1 to 4. * ³ represents the bonding site with a carbon atom.

* ⁴ represents the bonding site of the silica particle with the oxygen atom bonded to the silicon atom on the particle surface.

Component (a) having the structure represented by formula (3) introduces a surface modifying group derived from an organic alkoxysilane compound having an ethylenically unsaturated double bond group through a dehydration condensation reaction with a silanol group on the surface of the silica particle, , can be obtained by subjecting the ethylenically unsaturated double bond group contained in the surface modification group to radical polymerization using light and/or heat.

Examples of organic alkoxysilane compounds having an ethylenically unsaturated double bond group include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, and 3-methacryl. Oxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, Examples include 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

Component (a), whose reactive residue has a structure represented by formula (4), introduces a surface modifier derived from an isocyanate compound having an ethylenically unsaturated double bond group through a urethanation reaction with a silanol group on the surface of the silica particle. It can be obtained by subjecting the ethylenically unsaturated double bond group included in the surface modification group to radical polymerization using light and/or heat. Examples of the isocyanate compound having an ethylenically unsaturated double bond group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. You can.

In addition, by sequentially modifying the surface of the silica particles with a surface modifying group derived from an organic alkoxysilane compound having an ethylenically unsaturated double bond group and a surface modifying group derived from an isocyanate compound having an ethylenically unsaturated double bond group, a reaction occurs. Component (a), whose residues have the structure represented by formula (3) and the structure represented by formula (4), can be obtained.

For example, in order to improve the dispersion stability of component (a) in a negative photosensitive composition, component (a) preferably further has a trialkylsilyl group, and more preferably has a trimethylsilyl group. Trimethylsilyl group can be introduced into component (a) by converting hydrogen atoms in the surface silanol groups of the silica particles into trimethylsilyl groups using a trimethylsilylating agent. Examples of the trimethylsilylating agent include hexamethyldisilazane and trimethylalkoxysilane, which can be introduced through deammonification reaction and dehydration condensation reaction, respectively. By improving the dispersion stability of component (a), there are cases where luminance unevenness can be reduced more stably.

In order to further reduce the unevenness of brightness, it is preferable that component (a) contains silica particles having sodium atoms. Examples of the form in which the sodium atom exists include an ion (Na+) and a salt with a silanol group (Si-ONa). The content of sodium atoms is preferably 100 to 5000 ppm by weight in component (a). Silica particles having sodium atoms can be synthesized by reaction between strongly alkaline sodium silicate as a silicon source and mineral acid, which is a strong acid, under alkaline conditions. Additionally, the sodium atoms contained in the silica particles can be detected at the central portion corresponding to the intersection of the major axis and the minor axis when imaging the cross section of the primary particle using the TEM-EDX described above.

The content of component (a) is preferably 1 to 50% by weight, more preferably 5 to 20% by weight, in terms of SiO ₂ in the pixel division layer in suppressing unevenness of luminance. For all silica components in the pixel dividing layer, from the same viewpoint, 1 to 50% by weight is preferable in terms of SiO ₂ , and 7 to 30% by weight is more preferable. The content in terms of SiO ₂ as used herein refers to the content converted by excluding the weight of moisture in the silica particles, which fluctuates due to thermal history, based on the technical common sense of those skilled in the art.

In order to further reduce the unevenness of luminance, the pixel dividing layer in the organic EL display device of the present invention further contains 1 to 50 ppm by weight of (c) hafnium atoms (hereinafter sometimes referred to as the (c) component). It is desirable to do so. 1 to 30 ppm by weight is more preferable. The component (c) is an inorganic particle containing a hafnium atom, which is preferably contained in the pixel dividing layer.

(c) Inorganic particles containing the component include, for example, hafnium oxide (HfO ₂ ), complex oxides of metals other than hafnium and hafnium, solid solutions of oxides of metals other than hafnium and hafnium oxide, hafnium oxynitride, and hafnium oxides other than hafnium. Examples include complex oxynitrides of metals and hafnium, oxynitrides of metals other than hafnium, and solid solutions of hafnium oxynitride. Among them, hafnium oxide (HfO ₂ ) or a composite oxide of a metal other than hafnium and hafnium is preferable, and a composite oxide of zirconium and hafnium (ZrO ₂ -HfO ₂ ) is preferable because it is excellent in reducing the unevenness of luminance. It is more desirable.

As the inorganic particles containing the component (c), commercial products available in powder form can be used, for example, Hafnium oxide P, Copper R, Copper S (all of the above are manufactured by ATI METALS), hafnium oxide fine particles (Kojundo Chemical) (manufactured by Laboratory Co., Ltd.) can be mentioned. As another method, in the process of preparing a pigment dispersion containing component (b), which will be described later, the surface of the grinding media containing component (c) is wet-polished using mechanical energy, and the fine particles generated are codispersed with component (b). , component (c) may be contained in the pixel division layer finally obtained.

(c) The content of the component is determined by carving out a portion located in the range of 0.2 to 0.8 ㎛ from the outermost layer of the pixel division layer in the film depth direction, heating and incinerating it at a temperature of 800°C or higher using an electric furnace, and adding sulfuric acid, nitric acid, And the solution obtained by heating and dissolving with hydrofluoric acid and then heating and dissolving with dilute nitric acid can be used as an analysis sample and quantified by ICP (inductively coupled plasma) emission spectroscopy. As an analysis device, PS3520VDDII (manufactured by Hitachi High-Tech Science Corporation) can be used.

<(D) Coloring material>

When coloring is required from the viewpoint of light-shielding properties or anti-reflection, it is preferable that the photosensitive resin composition used in the present invention contains the coloring material (D). It is preferable that the photosensitive resin composition contains the coloring material (D), because the pixel split layer contains the coloring material (D), and each effect described later is obtained. (D) A coloring material is a compound that absorbs light of a specific wavelength, and in particular, refers to a compound that is colored by absorbing light of the wavelength of visible light (380 to 780 nm). (D) By containing a coloring material, the cured film obtained from the photosensitive resin composition can be colored, and the coloring property of coloring the light passing through the cured film of the photosensitive resin composition or the light reflected from the cured film of the photosensitive resin composition to a desired color. It can be granted. In addition, it is possible to provide light-shielding properties that block light of a wavelength absorbed by the coloring material (D) from light that passes through the cured film of the photosensitive resin composition or light reflected from the cured film of the photosensitive resin composition.

The content of the (D) coloring material used in the present invention is preferably 1% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more in the pixel dividing layer. If the content ratio is within the above range, light-shielding properties, coloring properties, or color matching properties can be improved. On the other hand, the content ratio is preferably 70% by weight or less, more preferably 65% by weight or less, and even more preferably 60% by weight or less. If the content ratio is within the above range, sensitivity during exposure can be improved.

(D) Coloring materials include (D1) organic pigments, (D2) inorganic pigments, and (D3) dyes that absorb light in the wavelength of visible light and are colored white, red, orange, yellow, green, blue, or purple. Known compounds may be mentioned. These coloring materials may be used in combination of two or more, and two or more colors may be combined. Combining two or more types is preferable because the obtained pixel division layer has the effects described later. By combining two or more colors, the color mixing property of coloring the light passing through the cured film of the photosensitive resin composition or the light reflected from the cured film of the photosensitive resin composition to desired color coordinates can be improved.

(D) Curing of the photosensitive resin composition by applying the (D1) organic pigment as a coloring material, such as transmitting or blocking light of a desired specific wavelength by changing the chemical structure or functional group conversion function characteristic of the (D1) organic pigment. Color matching can be improved by adjusting the transmission spectrum or absorption spectrum of the membrane. Details of such (D1) organic pigment will be described later.

(D) By applying the (D2) inorganic pigment as the coloring material, the heat resistance and weather resistance of the cured film of the photosensitive resin composition can be improved due to the excellent heat resistance and weather resistance characteristics of the (D2) inorganic pigment. (D2) Inorganic pigments include, for example, zirconium nitride, zirconium oxide, titanium oxide, barium carbonate, zinc oxide, zinc sulfide, soft white, calcium carbonate, barium sulfate, white carbon, alumina white, silicon dioxide, kaolin clay, talc, and bentonite. , Bengala, molybdenum red, molybdenum orange, chrome vermillion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, royal blue, cobalt blue. , cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, graphite or silver-tin alloy, or metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver. Examples include particulates, oxides, complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, or oxynitrides.

Among these, in order to keep the surface roughness (Ra1) of the pixel dividing layer from 1.0 nm to 50 nm, it is preferable to disperse an inorganic pigment with a large specific gravity such as zirconium nitride. As will be described later, this is because pigment precipitation is expected during development in the pixel division layer corresponding to the halftone exposure area. Inorganic pigments have problems such as pigment aggregation, thickening, and decreased sensitivity over time, but by setting the acid equivalent of component (a) to 200 g/mol or more and 500 g/mol or less, the exposed area, unexposed area, and halftone exposed area described later can be improved. Alkali solubility can be adjusted preferably. If the acid equivalent of component (a) is less than 200 g/mol, for example, when obtaining a cured film of a positive photosensitive resin composition, the alkali solubility of the unexposed area increases and the dissolution rate difference with the exposed area is small, so that a desired pattern cannot be formed. I can't. By setting the acid equivalent to 200 g/mol or more, the solubility of the unexposed area can be suppressed, and a pattern with less residue in the opening area due to adhesion of the eluate from the unexposed area can be formed. Additionally, by setting the acid equivalent of component (a) to 500 g/mol or less, the dispersion stabilization of the zirconium nitride particles is promoted, and a photosensitive resin composition with excellent storage stability can be obtained.

(D3) A dye refers to a compound that colors an object by chemical adsorption or strong interaction of substituents such as ionic groups or hydroxy groups in the dye with the surface structure of the object, and is generally soluble in solvents, etc. In addition, coloring with dyes has high coloring power and high color development efficiency because each molecule adsorbs with the object. Dyes include, for example, direct dyes, reactive dyes, sulphide dyes, vat dyes, sulphide dyes, acid dyes, metal-containing dyes, metal-containing acid dyes, basic dyes, mordant dyes, acid mordant dyes, disperse dyes, cationic dyes, or fluorescent dyes. It can be classified as whitening dye, etc. From the materials group, anthraquinone-based dyes, azo-based dyes, azine-based dyes, phthalocyanine-based dyes, methine-based dyes, oxazine-based dyes, quinoline-based dyes, indigo-based dyes, indigoide-based dyes, carbonium-based dyes, srene-based dyes, Examples include perinone-based dyes, perylene-based dyes, triarylmethane-based dyes, or xanthene-based dyes, but (C) from the viewpoint of solubility in organic solvents and heat resistance, anthraquinone-based dyes, azo-based dyes, azine-based dyes, and methine dyes. Based dyes, triarylmethane based dyes, and xanthene based dyes are preferred.

Among these, in order to set the surface roughness (Ra1) of the pixel dividing layer to 1.0 nm or more and 50 nm or less, it is preferable to contain (D3-1) a salt-forming compound consisting of an acidic dye and a basic dye as the coloring material (D). (D3-1) This is because, by containing a salt-forming compound consisting of an acidic dye and a basic dye, precipitation of the dye during development is expected in the pixel dividing layer corresponding to the halftone exposed area.

(D3-1) A salt-forming compound consisting of an acid dye and a basic dye is a compound obtained by reacting an acid dye and a basic dye. It is a compound obtained through a chemical (salt formation) reaction between an acidic dye with an anionic dye ion and a basic dye with a cationic dye ion, and is chemically stable.

An acidic dye is a compound having an acidic substituent such as a sulfo group or a carboxyl group in the dye molecule, or an anionic water-soluble dye that is a salt thereof. Additionally, acidic dyes include those that have acidic substituents such as sulfo groups or carboxyl groups and are classified as direct dyes. Among them, it is preferable that the acid dye contains a xanthene-based acid dye because it can reduce opening residues. Since the xanthene-based acid dye can reduce opening residues, it is more preferable to contain a rhodamine-based acid dye such as C.I. Acid Red 50, 52, and 289. Additionally, since the rhodamine-based acid dye can increase the blackness of the cured film, it is more preferable to contain C.I. Acid Red 52.

A basic dye is a compound or a salt thereof that has a basic group such as an amino group or an imino group in the molecule, and is a dye that becomes a cation in an aqueous solution. Among these, the basic dye preferably contains a triarylmethane-based basic dye because it can increase the blackness of the cured film. Since the triarylmethane-based basic dye can increase the blackness of the cured film, it is more preferable to contain C.I. Basic Blue 7 and/or C.I. Basic Blue 26.

Salt-forming compounds of acidic dyes and basic dyes can be synthesized by known methods. For example, when an aqueous solution of an acid dye and an aqueous solution of a basic dye are prepared separately and mixed slowly while stirring, a salt-forming compound of the acid dye and the basic dye is produced as a precipitate. By recovering this by filtration, the salt-forming compound can be obtained. It is preferable to dry the obtained salt-forming compound at about 60 to 70°C.

In addition, blackening can be achieved by setting the content of the salt-forming compound in the photosensitive resin composition to 10 parts by weight or more with respect to 100 parts by weight of the alkali-soluble resin (A), and opening residues can be reduced by setting it to 75 parts by weight or less. . By containing the salt-forming compound in this range, the alkali solubility of the exposed part, unexposed part, and halftone exposed part described later can be suitably adjusted.

Additionally, when it is desired to increase the blackness of the cured film, it is preferable to contain a nonionic dye (D3-2) as the (D) coloring material.

(D3-2) Nonionic dyes are dyes other than acid dyes and basic dyes and do not have an ionic structure.

Nonionic dyes include, for example, C.I. Dispers Orange 5; C. I. Dispers Red 58; C. I. Disperse Blue 165; C. I. Azo-based nonionic dyes such as Solvent Red 18; C. I. Bat Blue 4; C. I. Dispers Red 22, 60; C. I. Disperse Violet 26, 28, 31; C. I. dispers blue 14, 56, 60; C. I. Solvent Violet 13, 31, 36; C.I. Anthraquinone-based nonionic dyes such as Solvent Blue 35, 36, 45, 63, 78, 87, 97, 104, and 122, etc. can be mentioned.

Among them, an anthraquinone-based nonionic dye is preferable as the nonionic dye because it can increase the blackness of the cured film.

<(D1) Organic Pigment>

(D) Organic pigments (D1) used as coloring materials include, for example, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, pyranthrone-based pigments, dioxazine-based pigments, thioindigo-based pigments, and diketopyrrolopi. Roll-based pigments, quinophthalone-based pigments, srene-based pigments, indoline-based pigments, isoindoline-based pigments, isoindolinone-based pigments, benzofuranone-based pigments, perylene-based pigments, aniline-based pigments, azo-based pigments, azomethine-based pigments , condensed azo pigments, carbon black, metal complex pigments, lake pigments, toner pigments, or fluorescent pigments. From the viewpoint of heat resistance, anthraquinone-based pigments, quinacridone-based pigments, pyranthrone-based pigments, diketopyrrolopyrrole-based pigments, benzofuranone-based pigments, perylene-based pigments, condensed azo-based pigments, and carbon black are preferable.

In the present invention, from the effect of imparting light-shielding properties to the pixel split layer, it is preferable that the photosensitive resin composition used when forming the pixel split layer contains an organic pigment. It is preferable that the photosensitive resin composition contains an organic pigment because the pixel dividing layer contains the organic pigment and the effects described below are obtained. In this case, it is preferable to further contain an organic black pigment and/or a mixed-color organic black pigment (hereinafter sometimes referred to as (b) component) as the organic pigment (D1).

Examples of organic black pigments include benzodifuranone-based black pigments, perylene-based black pigments, and azomethine-based black pigments.

Examples of the benzodifuranone-based black pigment include the pigment disclosed in International Publication No. 2009/010521. Irgaphor Black (registered trademark) S0100CF and Experimental Black 582 (both manufactured by BASF SE) can be preferably used as a commercially available benzodifuranone-based black pigment consisting of a compound represented by formula (5) described later.

Examples of the perylene-based black pigment include C.I. Pigment Black 31, C.I. Pigment Black 32, perylenetetracarboxylic acid benzoimidazole or its derivatives, and the pigment disclosed in International Publication No. 2005/078023. As commercial products, Spectrasense (registered trademark) Black S0084, L0086, K0087, and K0088 (all manufactured by BASF SE) can be used.

Examples of the azomethine-based black pigment include the pigment disclosed in US Patent Application Publication No. 2002-121228. As a commercial product, CHROMOFINE BLACK A1103 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) can be used.

Mixed-color organic black pigment means (b-1) at least one organic pigment selected from organic yellow pigment, organic red pigment, and organic orange pigment (hereinafter sometimes referred to as (b-1) component) and ( b-2) Contains at least one color organic pigment (hereinafter sometimes referred to as (b-2) component) selected from organic blue pigment and organic purple pigment, and (b-1) component and (b-2) ) means a pigment mixture in which the content of component (b-2) is 20% by weight or more relative to the total amount of components.

Examples of organic yellow pigments include C.I. Pigment Yellow 24, 120, 138, 139, 151, 175, 180, 185, 181, 192, 193, and 194. Examples of organic orange pigments include C.I. Pigment Orange 13, 36, 43, 60, 61, 62, 64, 71, and 72. Examples of organic red pigments include C.I. Pigment Red 122, 123, 149, 178, 177, 179, 180, 189, 190, 202, 209, 254, 255, and 264. Organic blue pigments include, for example, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:6, 16, 25, 56, 57, 60, 61, 64, 65, 66, 75, Examples include 79 and 80. Examples of organic purple pigments include C.I. Pigment Violet 19, 23, 29, 32, and 37.

Among the components corresponding to component (b) above, in reducing unevenness of luminance, component (b) contained in the pixel dividing layer in the organic EL display device of the present invention contains an organic black pigment, and the organic black pigment It is preferable that the pigment contains the compound represented by formula (5) or formula (6) and/or its isomer. It is more preferable that the component (b) contained in the pixel dividing layer contains the compound represented by formula (7) or an isomer thereof. The compounds represented by formulas (5) to (7) are synthesized by reaction of 2,5-dihydroxy-1,4-benzene diacetic acid with isatin or its derivatives under an acidic catalyst, and then converted into pigments. You can get it.

In formulas (5) and (6), R ₂₂ ¹ to R ₃₁ ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

In order to further suppress unevenness of brightness, the component corresponding to component (b) may have been subjected to micronization treatment by a known method such as a solvent salt milling method or an acid paste method. When micronizing a benzodifuranone-based black pigment, it may become easy to suppress brightness unevenness by coexisting the compound represented by formula (8) or its salt and adsorbing it on the pigment surface.

In formula (8), n and m represent integers and are each independently 0 to 2. However, n+m≥1 is satisfied.

In addition, when component (b) contains a benzodifuranone-based black pigment, it is preferable to have a coating layer containing silica on the surface of the pigment in order to improve developability and suppress development residue in the opening. The silica contained in the coating layer herein is not the component (a) described above, but is considered a part of component (b).

The content of component (b) is preferably 1% by weight or more, and more preferably 10% by weight or more in the pixel dividing layer in order to achieve high light-shielding properties. In reducing unevenness of brightness, 50% by weight or less is preferable, and 30% by weight or less is more preferable.

In addition, when component (a) is further contained in addition to component (b), the content of component (a) relative to 100 parts by weight of component (b) is 20 to 70 weight in terms of SiO ₂ in reducing brightness unevenness. parts by weight is preferable, and 30 to 50 parts by weight is more preferable. That is, in the organic EL display device of the present invention, the content of component (a) relative to component (b) in the pixel division layer is preferably 20 to 70 parts by weight in terms of SiO ₂ .

<(E) Liquid-repellent material>

When forming the organic EL layer by an inkjet method, it is preferable that the photosensitive resin composition used in the present invention contains a liquid-repellent material. Although known materials such as fluorine-based polymers and fluorine-containing compounds having silane compounds can be used, liquid-repellent materials having at least an amide group or a urethane group are preferable. Having an amide group or a urethane group improves compatibility with the alkali-soluble resin (A) described above and has the effect of reducing defects such as bounce and improving film thickness uniformity of the cured film, resulting in poor display of the display device. reduce.

Examples of liquid-repellent materials include 2-(perfluorobutyl)ethyl(meth)acrylate, 2-(perfluorohexyl)ethyl(meth)acrylate, which are (meth)acrylate monomers having a perfluoroalkyl group, and commercial products. "MEGAFACE (registered trademark)" RS-72-K, RS-72-A, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 (manufactured by DIC Corporation), etc. I can hear it.

In addition, preferred examples of epoxy group-containing (meth)acrylate monomers include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutylacrylate glycidyl ether (4-HBAGE), and 4-hydroxybutyl metharylate. Examples include triglycidyl ether, acrylate having an alicyclic epoxy group, and metarylate having an alicyclic epoxy group.

The liquid-repellent material (E) having an amide group or a urethane group may be a copolymer obtained by copolymerizing (meth)acrylic monomers substituted with different functional groups. By copolymerizing different functional group-substituted (meth)acrylic monomers, it is possible to easily maintain a balance between liquid repellency and solubility. For example, (meth)acrylates containing hydroxyl groups, (meth)acrylamides containing hydroxyl groups, (meth)acrylates containing alkoxy groups, (meth)acrylates containing block isocyanate groups, (meth)acrylates containing phenoxy groups. Rates, alkyl (meth)acrylates, vinyl group-containing compounds, etc. can be mentioned. Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate. Examples of hydroxyl group-containing (meth)acrylamides include N-hydroxymethylacrylamide. Examples of (meth)acrylates having an alkoxy group include 3-methacryloxypropylmethyldimethoxysilane. Block isocyanate group-containing (meth)acrylates include, for example, 2-(0-[1'-methylpropylidenamino]carboxyamino)ethyl methacrylate (KARENZ MOI-BM: manufactured by Resonac Corporation; registered trademark), etc. can be mentioned. Examples of phenoxy group-containing (meth)acrylates include 2-phenoxybenzyl acrylate and 3-phenoxybenzyl acrylate. Alkyl (meth)acrylates may be unsubstituted or substituted with at least one of an amino group, monoalkylamino group, dialkylamino group, hydrocarbon aromatic ring, or heterocyclic ring, or may be linear or branched, with an acid anhydride cleavage added to the hydroxy group. , and/or a diluting monomer that is an unsubstituted or substituted alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms in a ring, for example, alkyl acrylate. Examples of vinyl group-containing compounds include n-butyl vinyl ether.

The compound contained in the liquid-repellent material (E) having an amide group or a urethane group is usually a (co)polymer. The (co)polymer as a compound contained in the liquid-repellent material (E) can be obtained by a known polymerization method. The (co)polymerization may be obtained, for example, by ionic polymerization such as radical polymerization or anionic polymerization. Additionally, it may be any one of random copolymers, block copolymers, and graft (co)polymers, or it may be mutual copolymers. Here, the radical (co)polymerization method is taken as an example. For example, a predetermined amount of dimethyl (meth)acrylamide, a predetermined amount of fluorine-containing (meth)acrylate monomer, and, if necessary, a predetermined amount of epoxy group-containing (meth)acrylates and hydroxyl group-containing (meth)acrylates. hydroxyl group-containing (meth)acrylamides, alkoxy group-containing (meth)acrylates, block isocyanate group-containing (meth)acrylates, phenoxy group-containing (meth)acrylates, alkyl (meth)acrylates, The liquid-repellent material (E) can be obtained by randomly copolymerizing vinyl group-containing compounds with a radical polymerization initiator in an appropriate solvent. During random copolymerization, a chain transfer agent may be added as needed. As a radical polymerization initiator, for example, tert-butylperoxy-2-ethylhexanoate can be used. As a chain transfer agent, for example, dodecyl mercaptan can be used. Additionally, as a solvent, for example, an inert solvent such as cyclohexanone can be used.

The weight average molecular weight of the liquid-repellent material (E) having an amide group or a urethane group is preferably in the range of 1,500 to 50,000. By setting the molecular weight within this range, it can be more easily dissolved in a solvent used in the photosensitive resin composition. In addition, setting the molecular weight within this range is preferable because the anti-foaming property of the photosensitive resin composition solution increases. The liquid-repellent material (E) having an amide group or a urethane group is preferably 0.1 part by weight or more, and 0.3 parts by weight or more, based on 100 parts by weight of the alkali-soluble resin (A), from the viewpoint of making it easy for the obtained cured film to sufficiently exhibit liquid repellency. It is more desirable. Furthermore, from the viewpoint of making it difficult to create liquid repellency in the pixel and making it easy to obtain high durability, 10 parts by weight or less is preferable, and 5 parts by weight or less is more preferable.

<Spacer>

In the organic EL display device of the present invention, the spacer 4 is installed on the pixel division layer. As a first purpose, by providing a spacer, the contact area between the substrate and the deposition mask when forming the organic EL layer can be reduced, thereby suppressing the generation of particles during the process. As a result, a decrease in the product ratio of the panel and deterioration of the light emitting element can be suppressed. In addition, as described above for the second purpose, it is necessary to fabricate a spacer on the pixel division layer to support the structure covering the second electrode in the post-process and to ensure the strength of the display device. As with the pixel division layer, patterning processing is essential for the spacer, and the residue from the removed area may be directly connected to defects such as short circuits and black spots. In addition, because the shape of the edge of the spacer may cause disconnection of the second electrode, workability such as a gentle forward taper shape is also required.

As the spacer, any material having the necessary mechanical or electrical properties can be used without particular limitation, and is not limited to any of known organic or inorganic materials. However, from the viewpoint of processability, a cured film of a photosensitive resin composition is preferable. Additionally, by forming the same material as the pixel division layer through batch processing, it is possible to achieve improved production rates and lower costs for panels with shorter process times.

As described above, the problem of separation between the pixel split layer and the organic EL layer is also a problem at the interface where the spacer and the organic EL layer are in contact. Therefore, in the present invention, the surface roughness (Ra1) of the pixel split layer and the surface roughness (Ra1) of the spacer are When Ramax is the maximum value of surface roughness (Ra2), Ramax is 1.0 nm or more and 50 nm or less. Additionally, it is more preferable that the surface roughness (Ra2) of the spacer is Ramax. Additionally, both the surface roughness (Ra1) of the pixel division layer and the surface roughness (Ra2) of the spacer may be Ramax. Additionally, the surface roughness of the spacer can be measured using atomic force microscopy (AFM) like the pixel division layer.

Additionally, since the spacer is formed on the outermost surface of the substrate, the surface of the spacer becomes an interface in contact with the organic EL layer. Conventionally, because the adhesion between the spacer and the organic EL layer was poor, peeling easily occurred, which was a major problem, especially for flexible products. In the present invention, the anchor effect can be obtained by setting the surface roughness (Ra2) of the spacer to 1.0 nm or more, and adhesion to the organic EL layer can be improved by preferably setting it to 5.0 nm or more, more preferably 20 nm or more. You can. Additionally, with respect to the surface roughness (Ra2) of the spacer, an anchor effect can be obtained if it is 1.0 nm or more, but for the purpose of suppressing pinholes in the second electrode and defects in the sealing process described later, it is preferable to set it to 50 nm or less. do. In addition, when improving adhesion by increasing Ra2, it is effective to ensure that the interface between the spacer and the organic EL layer is as large as possible, and Ra2 is larger than the surface roughness Ra1 of the pixel division layer described above, that is, Ra2 In the case of Ramax, it is preferable that the area of the interface between the spacer and the organic EL layer is 50% or more of the area of the interface between the substrate and the organic EL layer. This indicates that the spacer is more than 50% of the surface area of the substrate.

When Ra1 or Ra2 is large, such as 1.0 nm or more, in addition to the effect of improving adhesion, it is also possible to suppress external light reflection of the display device by increasing the diffused reflected light of the substrate. Generally, when external light is incident on a substrate, two types of reflected light, regular reflection and diffuse reflection, are generated on the surface of the substrate, and the total amount becomes the amount of reflected light, but what humans perceive as glare or reflection is regular reflected light. has a great influence. In other words, in order to maintain display quality as a display device, it is effective to increase the diffuse reflected light of the substrate and reduce the regular reflected light. In other words, by increasing Ra1 or Ra2, which is the surface roughness of the pixel division layer or spacer included in the surface of the substrate, to 1.0 nm or more, the diffuse reflected light on the substrate surface increases, which ultimately leads to securing the display quality of the display device.

Additionally, if the absolute value of the difference between Ra1 and Ra2 is 1.0 nm or more, two types of anchor effects are obtained, which is more preferable from the viewpoint of improved adhesion.

Additionally, depending on the shape of the edge of the spacer, it may cause disconnection of the second electrode, so it is preferable to have a gentle forward taper shape. Here, the forward tapered shape means that the angle formed by the tangent at the interface between the pixel division layer and the spacer and the tangent at the position of the film thickness of 50% of the maximum thickness of the spacer on the surface of the tapered portion of the spacer is 90°. It refers to a state of less than .

The thickness of the spacer is usually 0.3 μm to 10 μm, but is not particularly limited as long as it is sufficient to maintain the structure that contacts the deposition mask or covers the second electrode.

<Organic EL layer>

In the organic EL display device of the present invention, the structure of the organic EL layer 5 is not particularly limited, and for example, (1) hole transport layer/light-emitting layer, (2) hole transport layer/light-emitting layer/electron transport layer, (3) light-emitting layer/ It may be any one of the electron transport layers. Additionally, a tandem type may be used in which a plurality of the above configurations are laminated with charge generation layers. The charge generation layer is also generally called an electron extraction layer, a connection layer, an intermediate layer, an intermediate electrode, an intermediate conductive layer, and an intermediate insulating layer, and a known material composition can be used. The tandem type is preferable because improvements in emission luminance and emission lifetime can be expected. Specific examples of the tandem type include (4) hole transport layer/light-emitting layer/electron transport layer/charge generation layer/hole transport layer/light-emitting layer/electron transport layer, (5) hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection. Layer/charge generation layer/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer, (6) hole transport layer/light-emitting layer/electron transport layer/charge generation layer/hole transport layer/light-emitting layer/electron transport layer/charge generation layer/hole A laminated structure including a charge generation layer between an anode and a cathode, such as a transport layer/light-emitting layer/electron transport layer, can be given.

Additionally, each of the above layers may be either a single layer or multiple layers, and may be doped. In particular, it is preferable that the electron transport layer and the charge generation layer are metal doped layers, and the electron transport ability and the electron injection ability into other adjacent layers can be improved. Additionally, in addition to each of the above layers, a protective layer (cap layer) may be further provided, and the luminous efficiency can be further improved by the optical interference effect. The thickness of each layer is generally selected from 1 to 200 nm in consideration of the resistance value of each layer material and the influence on the extraction efficiency of EL light emission.

<Hole transport layer>

The hole transport layer is formed, for example, by a method of laminating or mixing one or two or more types of hole transport materials, or a method of using a mixture of a hole transport material and a polymer binder. Additionally, an inorganic salt such as iron (III) chloride may be added to the hole transport material to form a hole transport layer. The hole transport material is not particularly limited as long as it is a compound that forms a thin film necessary for manufacturing a light emitting device, can inject holes from an electrode serving as an anode, and can transport holes. The hole transport layer may be a single layer or may be composed of a plurality of layers stacked.

Suitable examples of hole transport materials include 4,4'-bis(N-(3-methylphenyl)-N-phenylamino)biphenyl, 4,4'-bis(N-(1-naphthyl)-N-phenylamino) Triphenylamine derivatives such as biphenyl, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, bis(N-allylcarbazole), bis(N-alkylcarbazole), etc. Heterocyclic compounds such as biscarbazole derivatives, pyrazoline derivatives, stilbene-based compounds, hydrazone-based compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, phthalocyanine derivatives, and porphyrin derivatives, and polymers having the above-mentioned monomer in the side chain. Examples include polycarbonate, styrene derivatives, polythiophene, polyaniline, polyfluorene, polyvinylcarbazole, and polysilane.

<Emitting layer>

In the light-emitting layer, injected electrons and holes recombine to emit light. A major feature of the organic EL display device is that various multi-colored light emission is possible by selecting the material constituting the light emitting layer.

The light-emitting layer is a layer in which a light-emitting material is excited and emits light by recombination energy resulting from collisions of holes and electrons. The light-emitting layer may be a single layer or may be composed of a plurality of layers stacked, and each light-emitting layer is formed of a light-emitting material (host material and/or dopant material). Each light-emitting layer may be composed of only one of the host material and the dopant material, or may be composed of a combination of one or more host materials and one or more dopant materials. That is, in each light-emitting layer, only the host material or the dopant material may emit light, or the host material and the dopant material may emit light together. From the viewpoint of efficiently using electrical energy and obtaining light emission with high color purity, it is preferable that the light emitting layer is composed of a combination of a host material and a dopant material. The dopant material may be contained entirely or partially in the host material.

From the viewpoint of suppressing the concentration quenching phenomenon, the content of the dopant material in the light-emitting layer is preferably 30 parts by weight or less, and more preferably 20 parts by weight or less, with respect to 100 parts by weight of the host material.

The light-emitting layer can be formed by a method of co-depositing a host material and a dopant material, or a method of mixing the host material and the dopant material in advance and then depositing them.

Host materials constituting the light-emitting material include, for example, compounds having a condensed aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene. etc. can be mentioned. You may use two or more of these. Hosts used when the light-emitting layer emits triplet light (phosphorescence) include metal chelated oxinoid compounds, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, indolocarbazole derivatives, triazine derivatives, and triphenyl derivatives. Ren derivatives and the like are suitably used. Among them, compounds having an anthracene skeleton or a pyrene skeleton are more preferable because highly efficient light emission is easily obtained.

Dopant materials constituting the light-emitting material include, for example, condensed ring derivatives such as anthracene and pyrene, metal complex compounds such as tris(8-quinolinolate)aluminum, and bistyryl anthracene derivatives and distyrylbenzene derivatives. Examples include reel derivatives, tetraphenylbutadiene derivatives, dibenzofuran derivatives, carbazole derivatives, indolocarbazole derivatives, and polyphenylenevinylene derivatives. Dopant materials used when the light-emitting layer emits triplet light (phosphorescence) include iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re). A metal complex compound containing at least one metal selected from the following is preferred. The ligand constituting the metal complex compound can be appropriately selected from the relationship between the required emission color, organic EL display device performance, and host compound, and preferably has a nitrogen-containing aromatic heterocycle such as a phenylpyridine skeleton, phenylquinoline skeleton, or carbene skeleton. do. Specifically, tris(2-phenylpyridyl)iridium complex, bis(2-phenylpyridyl)(acetylacetonate)iridium complex, tetraethylporphyrin platinum complex, etc. are mentioned. You may use two or more of these.

<Electron transport layer>

The electron transport layer is a layer that transports electrons injected from the cathode to the light-emitting layer. In order to achieve a low driving voltage, it is preferable that the organic EL layer of the present invention includes an electron transport layer. It is desired that the electron transport layer has high electron injection efficiency and transports the injected electrons efficiently. Therefore, it is desirable that the electron transport layer be made of a material that has high electron affinity and electron mobility, is excellent in stability, and impurities that become traps are unlikely to be generated during manufacture and use. In particular, when the film thickness is large, a compound with a molecular weight of 400 or more is preferable because low molecular weight compounds tend to crystallize and thus deteriorate the film quality. In addition, when considering the transport balance between holes and electrons, it is desirable for the electron transport layer to have a role of efficiently preventing unrecombined holes from flowing from the anode to the cathode, and the electron transport layer in the present invention contains holes. A hole blocking layer that can efficiently prevent movement is also included as a consent. The electron transport layer may be a single layer or may be composed of a plurality of layers stacked.

Examples of the electron transport material constituting the electron transport layer include condensed polycyclic aromatic derivatives such as naphthalene and anthracene. You may use two or more of these. Among these, compounds having a heteroaryl ring structure containing electron-accepting nitrogen are preferred because the driving voltage can be further reduced and high-efficiency light emission can be obtained.

Electron-accepting nitrogen as used herein refers to a nitrogen atom that forms multiple bonds with adjacent atoms. Since the nitrogen atom has high electronegativity, these multiple bonds have electron-accepting properties. Therefore, the aromatic heterocycle containing electron-accepting nitrogen has high electron affinity. The driving voltage can be further reduced because the electron transport material containing electron-accepting nitrogen easily receives electrons from the cathode with high electron affinity. Additionally, the supply of electrons to the light-emitting layer increases and the probability of recombination increases, thereby improving luminous efficiency.

Examples of heteroaryl rings containing electron-accepting nitrogen include triazine rings and pyridine rings. Compounds having these heteroaryl ring structures include triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, 2,5-bis(6'-(2',2") -Bipyridyl))-1,1-dimethyl-3,4-diphenylsilol and other bipyridine derivatives, 1,3-bis(4'-(2,2':6'2"-terpyridinyl) ) Terpyridine derivatives such as benzene are preferably used from the viewpoint of electron transport ability. You may use two or more of these.

Additionally, a compound having a phenanthroline skeleton can be cited as a material that satisfies the conditions required for the electron transport layer. In order to obtain stable light emission over a long period of time, a material with excellent thermal stability and thin film formation is required, and among compounds having a phenanthroline skeleton, the substituent itself has a three-dimensional structure or is adjacent to or adjacent to the phenanthroline skeleton. It is preferable to have a three-dimensional structure due to steric repulsion with substituents, or to have a plurality of phenanthroline skeletons linked together. Additionally, when connecting multiple phenanthroline skeletons, a compound containing a conjugate bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the connecting unit is more preferable.

The electron transport material does not need to be limited to only one type of compound having a phenanthroline skeleton. A plurality of the above compounds may be mixed and used, or one or more types of known electron transport materials may be mixed with the above compound. Known electron transport materials are not particularly limited, but include quinolinol derivative metal complexes such as 8-hydroxyquinoline aluminum, benzoquinoline metal complexes, tropolone metal complexes, flavonol metal complexes, perylene derivatives, and perinone derivatives. , naphthalene, coumarin derivatives, oxadiazole derivatives, aldazine derivatives, bistyryl derivatives, pyrazine derivatives, phenanthroline derivatives, quinoline derivatives, benzimidazole derivatives, triazole derivatives, quinoxaline derivatives, benzoquinoline derivatives, etc. There is no particular limitation. These electron transport materials can be used alone, but may be used by stacking or mixing them with different electron transport materials. Additionally, compounds having a nitrogen-containing aromatic heterocycle, such as phenanthroline derivatives and oligopyridine derivatives, can also be used. In particular, compounds having a phenanthroline skeleton, which will be described later, are preferred because they exhibit excellent electron transport ability.

The electron transport material may be used alone, but two or more types of the electron transport material may be mixed and used, and one or more other electron transport materials may be mixed with the electron transport material. Additionally, it is preferable that the electron transport layer in the present invention contains a donor dopant material. Here, the donor dopant material is a compound that facilitates electron injection from the cathode or electron injection layer into the electron transport layer by improving the electron injection barrier, and also improves the electrical conductivity of the electron transport layer. In the present invention, the donor dopant material preferably contains at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, inorganic salts of the above metals, and complexes of the above metals and organic substances. The donor dopant material is preferably a complex with an inorganic salt or an organic substance rather than a metal alone because it is easy to deposit in a vacuum and is excellent in handling, and because it is easy to handle in the air and the addition concentration is easy to adjust, the organic substance is preferred. A complex with is more preferable.

<Charge generation layer>

The charge generation layer is generally made of a double layer, and specifically, a pn junction type charge generation layer consisting of an n-type charge generation layer and a p-type charge generation layer can be used. The pn junction type charge generation layer generates charges or separates the charges into holes and electrons by applying a voltage in the organic EL layer, and injects these holes and electrons into the light emitting layer via the hole transport layer and the electron transport layer. Specifically, it functions as an intermediate charge generation layer for the plurality of light-emitting layers included in the organic EL 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 existing on the cathode side. Therefore, the luminance and luminous efficiency of the organic EL layer containing a plurality of light-emitting layers can be further improved, the driving voltage can be lowered, and the luminescence life of the organic EL layer can also be further improved. From this point of view, in the present invention, it is preferable that the organic EL layer includes a charge generation layer. In addition, as will be described later, in the present invention, the charge generation layer preferably contains a donor dopant material, and the donor dopant material is an alkali metal, an alkaline earth metal, a rare earth metal, an inorganic salt of the above metals, or the above metals. It is preferable to contain one or more types selected from the group consisting of complexes of organic substances.

The n-type charge generation layer is preferably made of an n-type dopant material and a host material, and known materials can be used. For example, an alkali metal, alkaline earth metal, or rare earth metal can be used as the n-type dopant material. Additionally, as a host material, compounds having a nitrogen-containing aromatic heterocycle, such as compounds having a phenanthroline skeleton and oligopyridine derivatives, can be used. In particular, compounds having a phenanthroline skeleton described later are preferred because they exhibit excellent properties as host materials for the n-type charge generation layer, and they may be used in combination.

The p-type charge generation layer is preferably made of a p-type dopant material and a host material, and known materials can be used. For example, as a p-type dopant material, tetrafluore-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), tetracyanoquinodimethane derivative, radialene derivative, iodine, FeCl ₃ , FeF ₃ , SbCl ₅ , etc. can be used. The p-type dopant material is preferably a radialene derivative. The host material is preferably an arylamine derivative.

<Compound having a phenanthroline skeleton>

In the present invention, the electron transport layer and/or the charge generation layer preferably contain a compound having a phenanthroline skeleton represented by the following general formula (1).

Here, R ₁ to R ₈ may be the same or different, and are selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, and a heterocyclic group. However, at least one of R ₁ , R ₃ , R ₆ , and R ₈ is selected from adamantyl group, norbornyl group, phenylvinyl group, β-naphthyl group, phenanthrene group, and pyrenyl group.

Furthermore, in the present invention, it is more preferable that the electron transport layer and/or the charge generation layer contain a compound having a phenanthroline skeleton represented by the following general formula (2).

Here, R ₉ to R ₁₆ may be the same or different, and are selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, a heterocyclic group, and X ₁ . However, at least one of R ₉ to R ₁₆ is X ₁ . n represents a natural number from 2 to 6. _and It is a linking unit that connects multiple n-valent phenanthroline skeletons.

In these substituents, an alkyl group refers to a saturated aliphatic hydrocarbon group such as, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group, even if it has a substituent. , you don’t have to have it. There is no particular limitation on the additional substituent when substituted, and examples include alkyl group, halogen, aryl group, heteroaryl group, etc. This point is also common to the description below. Additionally, the number of carbon atoms in the alkyl group is not particularly limited, but is preferably in the range of 1 to 20, more preferably 1 to 8, from the viewpoint of availability and cost. In addition, the cycloalkyl group refers to a saturated alicyclic hydrocarbon group such as, for example, cyclopropyl group, cyclohexyl group, norbornyl group, and adamantyl group, which may or may not have a substituent. The number of carbon atoms in the alkyl group portion is not particularly limited, but is preferably in the range of 3 to 20. Additionally, an aralkyl group refers to an aromatic hydrocarbon group through an aliphatic hydrocarbon such as a benzyl group or phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be unsubstituted or substituted. In addition, an alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond, such as a vinyl group, an allyl group, or a butadienyl group, and may be unsubstituted or substituted. In addition, the cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclopentenyl group, cyclopentadienyl group, or cyclohexene group, and may be unsubstituted or substituted. In addition, an alkynyl group refers to an unsaturated aliphatic hydrocarbon group containing a triple bond, such as an acetylenyl group, and may be unsubstituted or substituted. In addition, an alkoxy group refers to an aliphatic hydrocarbon group through an ether bond, such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. Additionally, an alkylthio group is one in which the oxygen atom of the ether bond of an alkoxy group is replaced with a sulfur atom. Additionally, an aryl ether group refers to an aromatic hydrocarbon group through an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may be unsubstituted or substituted. Additionally, an arylthioether group is one in which the oxygen atom of the ether bond of an arylether group is replaced with a sulfur atom. In addition, an aryl group refers to an aromatic hydrocarbon group such as a phenyl group, naphthyl group, biphenyl group, phenanthryl group, terphenyl group, and pyrenyl group, which may be unsubstituted or substituted. In addition, the heterocyclic group refers to, for example, an aliphatic ring having atoms other than carbon in the ring, such as a pyran ring, piperidine ring, or cyclic amide, which may or may not have a substituent. The number of carbon atoms in the heterocyclic group is not particularly limited, but is preferably in the range of 2 to 20. Halogen refers to fluorine, chlorine, bromine, and iodine. Haloalkane, haloalkene, and haloalkyne mean that part or all of the above-mentioned alkyl group, alkenyl group, and alkynyl group, such as trifluoromethyl group, are substituted with the above-mentioned halogen, and the remaining portion is substituted even if unsubstituted. It doesn't matter if there is. Aldehyde group, carbonyl group, ester group, carbamoyl group, and amino group include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, etc., and aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be unsubstituted. It doesn't matter if it's replaced. The silyl group refers to a silicon compound group such as trimethylsilyl group, which may be unsubstituted or substituted. The siloxanyl group refers to a silicon compound group through an ether bond, such as a trimethylsiloxanyl group, which may be unsubstituted or substituted. Additionally, a ring structure may be formed between adjacent substituents. The ring structure formed may be unsubstituted or substituted.

In addition, the substituent itself has a three-dimensional structure, or a three-dimensional structure is created through steric repulsion with the phenanthroline skeleton or adjacent substituents, so the compound containing the phenanthroline skeleton has low planarity and is difficult to crystallize. It becomes difficult to wake up, and a good amorphous thin film state can be maintained. The fact that the substituent itself has a three-dimensional three-dimensional structure refers to a bulky three-dimensional structure rather than a two-dimensional planar structure such as, for example, a t-butyl group, adamantyl group, or norbornyl group, and can be substituted or unsubstituted. Does not matter. In addition, a substituent that gives rise to a three-dimensional structure by steric repulsion with the phenanthroline skeleton or adjacent substituents, such as α-naphthyl group, phenanthrene group, mesityl group, etc., refers to the substituent group even if the substituent itself has a planar structure. This indicates that the plane of the substituent is in a different plane from the plane of the phenanthroline skeleton due to steric repulsion between the phenanthroline skeleton or its substituents and adjacent substituents. These can be examined using molecular models, computer chemistry, etc.

Additionally, by connecting a plurality of phenanthroline skeletons, the compound containing the phenanthroline skeleton becomes high molecular weight, increases the glass transition temperature, and also makes it difficult for crystallization to occur, thereby maintaining a good amorphous thin film state.

Among the compounds having the phenanthroline skeleton of general formula (1) in the present invention, it is more suitable to introduce substituents at the 2nd, 4th, 7th, and 9th positions of the phenanthroline skeleton. These substituents are the same as described above. Specific examples of the compound having the phenanthroline skeleton include, but are not limited to, the following structures.

The host material of the electron transport layer and/or charge generation layer need not be limited to only one compound having a phenanthroline skeleton, and a mixture of compounds having a plurality of phenanthroline skeletons may be used, or one type of known host material may be used. The above may be mixed and used with a compound having a phenanthroline skeleton. The known host material is not particularly limited, but includes previously known condensed ring derivatives such as anthracene, phenanthrene, pyrene, perylene, and chrysene, and quinolinol derivatives such as tris(8-quinolinolato)aluminum. Metal complexes, benzoxazole derivatives, stilbene derivatives, benzthiazole derivatives, thiadiazole derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, oxadiazole derivatives, bistyrylanthracene derivatives or distyrylbenzene. Derivatives such as bistyryl derivatives, quinolinol derivatives and metal complexes combining different ligands, oxadiazole derivative metal complexes, benzazole derivative metal complexes, coumarin derivatives, pyrrolopyridine derivatives, perinone derivatives, thiadiazolopyridine In derivatives and polymers, polyphenylenevinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives can be used.

In addition, a compound having a phenanthroline skeleton may be used as a dopant material, but it is preferable to use it as a host material because it has excellent electron transport ability.

<Second electrode>

In the present invention, the second electrode 6 must be a light-reflective electrode in the case of the bottom emission type, and a light-transmissive electrode in the case of the top emission type.

In the case of the bottom emission type, a material that exhibits high reflectance of visible light above a certain film thickness and low electrical resistance is preferable, and Ag or an Ag alloy film mainly containing Ag is useful because it has a high reflectance. The Ag alloy film may use an MgAg alloy whose main component is Ag. Additionally, Al or an Al alloy film mainly containing Al is also good as a second electrode for bottom emission. An AlCr alloy film containing Cr or an AlNi alloy film containing Ni is preferable because it has a high reflectance at the level of pure Al and can also achieve low electrical resistance.

If it is a top emission type, for example, a conductive metal oxide such as transparent tin oxide, indium oxide, or indium tin oxide (ITO) can be used. However, to avoid damage to the organic EL layer, a thin film of MgAg alloy that can be produced by vapor deposition is used. desirable.

The resistance of the second electrode is not limited, as is the case with the first electrode, as long as it can supply sufficient current for light emission of the light-emitting element, but it is preferably low in resistance from the viewpoint of power consumption of the light-emitting element. The thickness of the electrode can be selected arbitrarily according to characteristics such as transmittance and resistance value, but it can be used between 100 and 300 nm for the bottom emission type and 10 to 30 nm for the top emission type.

<Wiring, TFT>

In the present invention, as described above, a driving circuit such as wiring or TFT 7 may be formed as included in the base material 1.

When the organic EL display device is an active drive type top emission type, the patterned island-shaped first electrode 2 is often connected to the TFT 7 formed in advance as a part of the substrate 1.

The semiconductor layer of the TFT is oxides such as a-Si (amorphous silicon), p-Si (polycrystalline silicon), microcrystal silicon, In-Ga-Zn-O, and LTPO (Low Temperature) using a combination of p-Si and oxide. Polycrystalline Oxide), etc., but generally two types are used: a-SiTFT and p-SiTFT. While a-SiTFT has a low mobility, which is an indicator of the ease of movement of electrons, the manufacturing process is relatively short and it can be manufactured on large substrates, so it can be used for a wide range of small to large displays. On the other hand, p-SiTFT has high mobility, and driver circuits, etc. can be formed on the substrate. The manufacturing process is longer than that of a-Si, and the difficulty of manufacturing is high on large substrates, so it is preferable to mainly use it for small and medium-sized displays. In particular, p-Si in p-SiTFT can generally be formed by using a-Si as a starting film and irradiating laser light to instantaneously melt and crystallize. Additionally, in the manufacturing process of a-SiTFT, there is a process called doping in which unused phosphorus or boron is injected into Si, and the threshold of TFT characteristics may be controlled by doping impurities into the Si film.

If TFTs are broadly classified based on their structure, they can be classified into bottom gate type and top gate type. It is preferable to use a bottom gate type for a-SiTFT and a top gate type for p-SiTFT. For example, in the top gate type, the drain side electrode and the source side electrode are connected to the semiconductor layer, and the gate electrode is formed above the semiconductor layer. TFTs are formed on a substrate by repeating the element processes of thin film formation, patterning, etching, and cleaning several times. A known method can be used to form the TFT. Additionally, in the bottom gate type, the gate electrode is disposed on the lowest layer, the semiconductor layer/insulating film is on the upper layer, and the source electrode and drain electrode are formed on the upper layer. When the gate electrode, source electrode, and drain electrode are connected with a straight line, an inverted triangle may be formed, which may also be called an “inverted stagger structure.”

<Planarization layer>

In particular, in the case of active drive type, for example, as shown in FIG. 2, when wiring or TFT 7 is formed inside the base material 1, it is preferable to use the planarization layer 8. By forming the planarization layer 8, the unevenness of the wiring or TFT 7 can be covered and planarized. In this case, since the first electrode 2 is formed on the planarization layer, it is desirable to connect the first electrode 2 and the wiring or TFT 7 through a contact hole formed in the planarization layer 8. The planarization layer 8 is not limited to either a known organic material or an inorganic material, but preferably includes a cured film of a photosensitive resin composition from the viewpoint of processability. The planarization layer 8 can be applied by a wet coating method such as spin coating, slit coating, dip coating, spray coating, or printing that can uniformly form a thin film on a base substrate.

The photosensitive resin composition preferably contains (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) an organic solvent, and may further contain a coloring material (D). By containing a combination of (A) an alkali-soluble resin and (B) a photosensitive agent as a photosensitive resin composition, pattern processing using photosensitivity becomes possible. Moreover, by containing (C) an organic solvent, it can be made into a varnish state and applicability can be improved in some cases. Additionally, the planarization layer can be blackened by the photosensitive resin composition containing the coloring material (D). The photosensitive resin composition may further contain other components.

(A) Materials of the alkali-soluble resin include, for example, acrylic resin, epoxy resin, polyamide resin, siloxane resin, and precursors of these resins, and the film thickness is not particularly limited as long as it is sufficient to cover the unevenness. . When coloring is required from the viewpoint of light blocking properties or anti-reflection, it is preferable to contain a coloring material appropriately.

<Sealing layer>

After forming the second electrode, it is preferable to seal it with a sealing layer 9, for example, as shown in FIG. 5. This is because organic EL light-emitting elements are said to be weak to oxygen and moisture, and in order to obtain a highly reliable display device, it is desirable to perform sealing in an atmosphere with as little oxygen and moisture as possible. It is also desirable to select a member with high gas barrier properties for the member used in the sealing layer 9, and similarly to the base material 1, it is appropriately selected from glass, resin film, gas barrier film, etc. For example, examples of gas barrier films include materials such as SiO ₂ (silicon oxide), SiN (silicon nitride), and SiON (silicon oxynitride). In addition, the sealing layer 9 made of a resin material such as acrylic resin or silicone resin may be formed on a layer formed using a material such as SiO ₂ (silicon oxide), SiN (silicon nitride), or SiON (silicon oxynitride). good night. In the case of a top emission type display device, it is preferably made of a light-transmissive material.

In addition, when adhesion is required, the adhesive used also needs to have high gas barrier properties, but generally, such as two-component epoxy adhesive (XNR, manufactured by Nagase ChemteX Corporation) or sealant for organic devices (MOISTURE CUT, manufactured by MORESCO Corporation), Any known method may be selected, and a method of melting the frit glass in the peripheral portion of the display device with a laser may be used.

Additionally, as a consideration for moisture, it is also effective to introduce a desiccant in the sealing process. As a desiccant, barium oxide, calcium oxide, etc. are known, but it is not particularly limited as long as the moisture adsorption performance is high.

<Polarizing layer>

The organic EL display device of the present invention preferably further includes a polarizing layer 10, as shown in Fig. 5, for example. Specifically, a linear polarization layer and a λ/4 phase difference layer are stacked, and reflection of light incident on the display device from the outside is suppressed. The linear polarizing layer is not particularly limited, but for example, a film obtained by dyeing a polyvinyl alcohol-based film with iodine and stretching it uniaxially is often used. The material constituting the λ/4 phase difference layer is not particularly limited, but a heat-resistant polyimide resin or the like is preferable.

<UV absorbing layer>

The organic EL display device of the present invention preferably further includes an ultraviolet ray absorption layer 11, as shown in Fig. 5, for example. By having the ultraviolet ray absorption layer 11, deterioration of the substrate and the organic EL layer 5 due to ultraviolet rays can be suppressed, and the reliability of the display device can be improved. As the ultraviolet absorption layer 11, a layer that absorbs light with a wavelength of 320 nm or less is preferable, a layer that absorbs light with a wavelength of 360 nm or less is more preferable, and a layer that absorbs light with a wavelength of 420 nm or less is still more preferable. However, since light with a wavelength of 420 nm or more overlaps with the blue emission wavelength used for display, the ultraviolet absorbing layer 11 preferably has a high transmittance in the region with a wavelength of 420 nm or more. This is particularly effective when the organic EL display device of the present invention is used outdoors.

The ultraviolet absorbing layer 11 is made of polyimide resin, polyamide resin, polyamideimide resin, polycarbonate resin, polyester resin, polyethersulfone resin, polyarylate resin, polyolefin resin, polyethylene terephthalate resin, and polymethyl methacrylate. It is preferable to contain resins such as polysulfone resin, polyethylene resin, polyvinyl chloride resin, alicyclic olefin polymer resin, acrylic polymer resin, and cellulose ester resin. You may contain two or more of these. Among these, polyimide resin and polyamide resin are more preferable.

The ultraviolet absorbing layer 11 may contain an ultraviolet absorber. UV absorbers include benzophenone-based compounds, oxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, salicylic acid ester-based compounds, acrylnitrile-based compounds, cyanoacrylate-based compounds, hindered amine-based compounds, and triazine-based compounds. compounds, nickel complex salt compounds, ultrafine titanium oxide, metal complex salt compounds, and other known polymer ultraviolet absorbers. You may contain two or more of these. Since the ultraviolet absorber has excellent transparency, benzotriazole-based compounds and benzophenone-based compounds are preferable, and benzotriazole-based compounds are more preferable.

As a polymer ultraviolet absorber, for example, a reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd. can be copolymerized with an acrylic monomer.

<Method for manufacturing organic EL display device>

The manufacturing method of the organic EL display device of the present invention includes a substrate having a first electrode 2, a pixel dividing layer 3, and a spacer 4 on a substrate 1, and an organic EL layer 5 and a second electrode. A manufacturing method of an organic EL display device having (6), comprising a step of batch processing the pixel split layer (3) and the spacer (4), wherein a photomask for batch processing has a light transmitting portion, a light blocking portion, and a semi-transmissive portion. It is a halftone photomask.

An example of the manufacturing method of the organic EL display device of the present invention will be described using the case of manufacturing the top emission type organic EL display device in FIG. 5 as an example.

First, wiring and the TFT 7 are formed on a base material that is a resin film. As a process, in addition to the TFT formation process such as “gate electrode formation process”, “gate insulating film formation process”, “Si film formation process”, and “source, drain electrode formation process”, wiring is placed to ensure electrical connection. However, all can be formed using known methods.

Next, the planarization layer 8 is applied by a slit coating method, formed into a film, and cured by heating. At this time, a contact hole is formed for the purpose of connection with the first electrode 2, but if the material used as the planarization layer 8 is photosensitive, it is photolithographically processed, and if it is not photosensitive, it is used as a general process using a resist material as a mask. This can be handled by etching processing. In this way, the base (1) is completed.

Subsequently, AgPdCu and ITO are sequentially deposited on the substrate as the first electrode 2, and patterning is performed to form the first electrode 2.

The manufacturing method of the organic EL display device of the present invention forms a pixel split layer (3) in the gap of the first electrode (2) and further forms a spacer (4) on the pixel split layer. As a process, after applying photosensitive resin to the entire surface, an opening is formed on the first electrode through photolithography processing, and the opening becomes a display pixel.

The manufacturing method of the organic EL display device of the present invention includes forming the pixel split layer 3 and the spacer 4 on the pixel split layer by batch processing, and forming the pixel split layer 3 and the spacer 4. The photomask for batch processing needs to be a halftone photomask having a light transmitting part, a light blocking part, and a semi-transmissive part. Generally, when performing processing using photosensitivity, a full-tone mask composed of a light-shielding portion and a light-transmitting portion is used. However, the halftone photomask used in the present invention includes a light-transmitting portion 12 and a light-shielding portion as shown in FIG. 6, for example. In addition to having a pattern including (14), the transmittance between the light transmitting portion 12 and the light blocking portion 14 is lower than the value of the light transmitting portion 12, and the transmittance is higher than the value of the light transmitting portion 14. It refers to a photomask having a semi-transmissive portion (13). By exposing using a halftone photomask, it becomes possible to form a pattern with a step shape after development and heat curing. In addition, when the photosensitive resin composition is a positive type, the exposed portion irradiated with active actinic rays by the light transmitting portion develops alkali solubility and becomes an opening, and the unexposed portion not irradiated with active actinic rays by the light shielding portion becomes a thick film. , corresponds to the spacer 4, and the halftone exposed portion irradiated with active actinic rays through the semi-transmissive portion corresponds to the pixel division layer 3 whose film thickness is smaller than that of the spacer 4. Conversely, when the photosensitive resin composition is a negative type, the cured portion irradiated with active actinic rays through the light transmitting portion corresponds to the spacer 4, and the halftone exposure portion irradiated with active actinic rays through the semi-transmissive portion corresponds to the pixel division layer 3. ) is equivalent to

As will be described later, as a halftone photomask used in the present invention, it is preferable that the transmittance of the semi-transmissive portion is 15 to 50% of the transmittance of the translucent portion. When the transmittance of the translucent portion is (%TFT), the transmittance (%THT) of the semi-transmissive portion is preferably 15% or more, and more preferably 20% or more of (%TFT). If the transmittance (%THT) of the semi-transparent portion is within the above range, the exposure amount when forming a cured pattern having a step shape can be reduced, thereby enabling shortening of the tact time. Meanwhile, the transmittance (%THT) of the semi-transparent portion is preferably 50% or less of (%TFT), and more preferably 45% or less. If the transmittance (%THT) of the semi-transmissive portion is within the above range, the film thickness difference between the spacer 4 and the pixel dividing layer 3 can be sufficiently increased, thereby improving the reliability of the display device. Furthermore, if the transmittance of the semi-transmissive portion is in the above range, a sufficient amount of active actinic ray exposure cannot be obtained in the semi-transmissive portion during patterning processing of the photosensitive resin composition, and the pixel division layer 3 and Differences occur in the surface roughness of the spacer 4. In this way, by differentiating the absolute value of the difference between the surface roughness Ra1 of the pixel dividing layer 3 and the surface roughness Ra2 of the spacer 4, two types of anchor effects are obtained as described above, and adhesion is improved. achieve In order to effectively obtain the anchor effect, it is desirable to ensure that the difference between Ra1 and Ra2 is 1.0 nm or more. In addition to the transmittance of the semi-transparent portion, both Ra1 and Ra2 can be adjusted by adjusting the resin composition, such as including a coloring material or a liquid-repellent material in the photosensitive resin composition.

In addition to the process using the halftone photomask described above, several methods can be combined, such as mechanical polishing using an abrasive, shot blasting or wet blasting by spraying an abrasive, and dry etching treatment such as plasma treatment or RIE. Although it is possible to adjust the surface roughness, in the present invention, it is necessary to use a halftone photomask to ensure that the absolute value of the difference between Ra1 and Ra2 is 1.0 nm or more.

In the method for manufacturing an organic EL display device of the present invention, a cleaning step may be included before the step of forming the organic EL layer 5 described later. In general, since there are many cases where contamination from previous processes such as photolithography processing remains on the surface of the first electrode, wet or dry cleaning is effective. Wet cleaning can be done using organic solvents, surfactants, water, acid solutions, alkaline solutions, etc., and can be selected from immersion, ultrasonic cleaning, boiling cleaning, etc. Additionally, in the case of dry cleaning, you can select from glow discharge treatment, plasma discharge treatment, UV/ozone treatment, etc. Dry cleaning using an oxygen atmosphere allows removal of contaminants and adjustment of work function. By adjusting the characteristics of the first electrode 2, the carrier injection efficiency from the first electrode 2 to the adjacent organic EL layer 5 is increased, and as a result, the characteristics of the display device, such as luminous efficiency and reliability, are likely to be improved. Lose.

Continuing, the manufacturing method of the organic EL display device of the present invention includes a step of forming the organic EL layer 5. Each layer, such as a hole transport layer, a light-emitting layer, and an electron transport layer, which constitute the organic EL layer 5, can be formed by a known method, for example, by a mask deposition method or an inkjet method.

The mask deposition method is a method of depositing and patterning an organic compound using a deposition mask, for example, a method of depositing by placing a deposition mask with a desired pattern as an opening on the deposition source side of the substrate. In order to obtain a high-precision deposition pattern, it is important to adhere a highly flat deposition mask to the substrate. Generally, a technique is used to apply tension to the deposition mask or to adhere the deposition mask to the substrate using a magnet placed on the back of the substrate. etc. can be used. However, since the generation of particles due to contact between the substrate and the deposition mask leads to a decrease in the product ratio of the panel and deterioration of the light emitting element, it is better to keep the spacer 4 in contact with the deposition mask as small as possible. desirable.

Methods for producing a deposition mask include etching, mechanical polishing, sand blasting, sintering, laser processing, use of photosensitive resin, and electroforming. However, when a fine pattern is required, etching or electroforming with excellent processing precision can be used. It is desirable to use

Since the mask deposition method or inkjet method becomes more difficult as the pattern becomes more detailed, it is required to employ the minimum necessary amount, for example, of a light-emitting layer that determines the light-emitting color. In this case, for example, by making the hole transport layer and electron transport layer other than the light emitting layer common to each color, it is allowed to form a film on the entire surface, thereby improving the product ratio and reducing the cost of the panel.

The manufacturing method of the organic EL display device of the present invention further includes a step of forming the second electrode 6. Although known methods can be used for the formation method, vacuum deposition is preferable because it is easy to avoid deterioration or damage to the underlying organic EL layer 5.

In the method of manufacturing the organic EL display device of FIG. 5, after the step of forming the second electrode 6, the sealing layer 9, the polarizing layer 10, and the ultraviolet absorbing layer 11 are sequentially laminated. Each layer can be formed by a known method, and as described above, the organic EL display device of FIG. 5 is completed.

(Example)

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

In each of the following evaluations, for cases where the test n number was not described, the evaluation was performed with n = 1.

<Measurement of film thickness of pixel division layer and spacer, observation of taper>

The film thickness of the pixel division layer and the spacer in each example and comparative example was determined from the level difference between the pixel division layer and the spacer on the patterned substrate (100 mm × 100 mm) using a surface roughness measuring device (SURFCOM 1400D, TOKYO SEIMITSU CO. ., LTD.) was used to measure it. The shape of the taper was observed through a scanning electron microscope (SEM, S-3000N, manufactured by Hitachi High-Tech Corporation) on a cross section of a patterned substrate.

<Surface roughness of pixel division layer and spacer>

The surface roughness of the pixel separation layer and spacer in each example and comparative example was determined by examining the pixel separation layer and spacer of a patterned substrate (100 mm × 100 mm) using an atomic force microscope (AFM, Dimension Icon, Bruker Corporation). Among the observed results, the arithmetic average roughness (Ra) was adopted. Observation conditions were RTESP-300 probe, tapping mode, scan size of 5 ㎛□, scan rate of 0.1 Hz, and number of sample lines were 1024.

<Observation of silica particles included in the pixel division layer>

The silica particles contained in the pixel dividing layer in each Example and Comparative Example were imaged using a transmission electron microscope-energy dispersive It was measured using a distribution measuring device (Mac-View, manufactured by MOUNTECH Co., Ltd.). That is, in the cross section of the pixel division layer of the patterned substrate (100 mm The minor axis and aspect ratio were measured, and silica particles with a major axis (nm) of 5 to 30 nm and an aspect ratio in the range of 1.0 to 1.5 were defined as component (a). In addition, for one silica particle, if the minor axis and major axis in the TEM image were the same, that is, if it was a perfect circle, the diameter was regarded as the major axis. Representative values representing the characteristics of silica particles corresponding to component (a) are the average value of the primary particle diameter, i.e., the average value of the major axis, calculated and rounded to one decimal place, and the average value of the aspect ratio, i.e. (a) The average value of the aspect ratio of each silica particle corresponding to the component was calculated, and the value rounded to 2 decimal places was used.

The presence or absence of component (a) in each example and comparative example is shown in Table 10, with A indicating the presence of the component (a) and B indicating the absence of the component (a). Examples 23 and 24 in which the component (a) was present. The cross-sectional analysis results of , 25 are shown in Table 11.

<Diffuse reflected light measurement>

The diffused reflected light of the substrate in each example and comparative example was measured by measuring the surface of the patterned substrate (100 mm .J) was measured, and the diffuse reflectance at a wavelength of 550 nm in SCE mode, which removes regular reflection light, was adopted. It was said that the higher the diffuse reflectance, the better the ability to suppress regular reflected light, so the characteristics were judged to be good.

<Adhesion test>

As shown in FIG. 7, the adhesion test of the organic EL display device in each Example and Comparative Example was performed on a substrate (100 mm A metal cylinder of ㎜ is fixed, and a bending operation is repeatedly performed along this cylinder in a range from the cylinder's wrap angle of 0° (when the substrate is flat) to the cylinder's wrap angle of 180° (when the cylinder is folded back). , the bends were observed under an optical microscope. Those in which peeling occurred between 1 and 100 bending operations were judged to be characteristic (C) due to low adhesion, those with 101 to 1000 bending operations were judged to be characteristic (B), and those with 1001 or more bending operations were judged to be characteristic (A) due to high adhesion. In addition, the test was performed 10 times (test n number 10), and the result with the smallest number of times until peeling occurred was adopted.

<Weather reliability test>

The weathering reliability test of the organic EL display device in each example and comparative example confirmed the appearance of the organic EL display device manufactured in each example and comparative example described later after being left for 24 hours at room temperature 23°C and humidity 45%. . 10 display devices were put into the test (test n number: 10), and if corrosion was not observed on the second electrode, the weather resistance reliability was good (A). If corrosion was observed on even one device, there was a pinhole in the second electrode. As such, it was decided as (B).

<Electrical reliability test>

The electrical reliability test of the organic EL display device in each Example and Comparative Example was conducted by testing the organic EL display device manufactured in each Example and Comparative Example described later by measuring a voltage of 5V between two adjacent stripe-shaped first electrodes. The current value when applied was measured. A source meter (2400, manufactured by Keithley Instruments, Inc.) was used for the measurement, and the smaller the current value, the smaller the leakage current, so the characteristics were judged to be good. In addition, the test was conducted at 20 locations (n. of tests was 20), and the average value of 10 measurements was adopted, excluding 5 large and small measurements.

<Luminous characteristics test>

The luminescence characteristic test of the organic EL display device in each example and comparative example was performed by selecting a pair of crossing first and second electrodes in the organic EL display device manufactured in each example and comparative example described later. The voltage and luminance when a current of 10 mA/cm2 was passed through one light emitting element were measured. A source meter (2400, manufactured by Keithley Instruments, Inc.) was used to measure voltage, and a spectroradiometer (CS-1000, manufactured by KONICA MINOLTA, Inc.) was used to measure luminance.

<Design of the first electrode and halftone photomask>

The design of the first electrode and halftone photomask in each example and comparative example is shown in FIG. 6. As shown in FIG. 6A, 100 first electrodes 2 were manufactured in the form of stripes with a line width of 60 μm, a pitch of 100 μm, and a length of 10 mm in the central part of the substrate 1 (100 mm × 100 mm). That is, the exposed portion of the substrate 1 is 40 μm wide. In contrast, in the positive halftone photomask (b), each line width was adjusted at a pitch of 100 μm so that the light-shielding portion 14 served as a spacer and the semi-transmissive portion 13 served as a pixel dividing layer. In the negative halftone photomask (c), the line widths (I and II) were adjusted so that the light-transmissive portion 12 was a spacer and the semi-transmissive portion 13 was a pixel dividing layer. In either case, alignment was performed as shown in FIG. 6 so that the pixel division layer and the spacer were disposed in the gap of the first electrode. In the completed substrate, the line width (I) corresponds to the interface where the pixel division layer and the organic EL layer contact, and the line width (II) corresponds to the interface where the spacer contacts the organic EL layer.

<Preparation of photosensitive resin composition>

Photosensitive resin compositions R-1 to R-15 used in each Example and Comparative Example were prepared as follows. In addition, among the compounds used, the names of those for which abbreviations are used are shown below.

BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

BFE: 1,2-bis(4-formylphenyl)ethane

BIP-PHBZ: 4,4',4"-methylidine trisphenol (manufactured by ASAHI YUKIZAI CORPORATION)

BYK-333: Silicone-based surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie GmbH)

DAE: Diaminodiphenyl ether

DFA: N,N-dimethylformamidedimethylacetal

DMAA: N,N-dimethylacrylamide

DPCA-60: Caprolactone 6 mol modified dipentaerythritol hexaacrylate (a hexafunctional acrylate with 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.)

EL: ethyl lactate

FAMAC-6: 2-(perfluorohexyl)ethyl methacrylate

GBL: γ-butyrolactone

GMA: Glycidyl methacrylate

HA: diamine compound containing hydroxy group

HMOM-TPHAP: A compound represented by the following formula having a phenolic hydroxyl group and substituents with a molecular weight of 40 or more at both ortho positions of the phenolic hydroxyl group (manufactured by Honshu Chemical Industry Co., Ltd.)

KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

MAP: 3-aminophenol; meta-aminophenol

MBA: 3-methoxy-n-butylacetate

MEK-ST-40: Silica particle dispersion (manufactured by Nissan Chemical Corporation). The solvent species is methyl ethyl ketone.

MEK-ST-L: Silica particle dispersion (manufactured by Nissan Chemical Corporation). The solvent species is methyl ethyl ketone.

MeTMS: Methyltrimethoxysilane

NA: 5-norbornene-2,3-dicarboxylic anhydride; nadic anhydride

TMOS: Tetramethoxysilane

NCI-831: "ADEKA ARKLS" (registered trademark) NCI-831 (made by ADEKA CORPORATION)

NMP: N-methyl-2-pyrrolidone

ODPA: bis(3,4-dicarboxyphenyl)ether dianhydride; Oxidiphthalic dianhydride

OSCAL-1421: Silica particle dispersion (manufactured by JGC Catalysts and Chemicals Ltd.). The solvent is isopropyl alcohol.

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

PhTMS: phenyltrimethoxysilane

S0100CF: Irgaphor Black (registered trademark) S0100CF

SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

S-20000: "SOLSPERSE" (registered trademark) 20000 (polyether-based dispersant, manufactured by Lubrizol Corporation)

TMSSucA: 3-trimethoxysilylpropylsuccinic anhydride

TrisP-PA: 1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane (Honshu Chemical Industry Co., Ltd. my)

WR-301: “ADEKA ARKLS” (registered trademark) WR-301 (made by ADEKA CORPORATION)

KARENZ MOI-BM: 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate

Bisphenol AF: 2,2-bis(4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd.)

6FDA: 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4'-Hexafluoropropane-2,2-diyl-bis(1,2-phthalic anhydride)

Pigment Dispersant 1: Pigment Dispersant 1 (solid content 100% by weight) disclosed in Synthesis Example 2 of Japanese Patent Application Laid-Open No. 2020/70352. A polymer-type dispersant with a linear polyalkylene amine structure and a polyether polymer chain.

<Synthesis Example 1 Synthesis of polyimide resin (PI-1)>

Under a dry nitrogen stream, 31.13 g (0.085 mol; 77.3 mol% of structural units derived from all amines and their derivatives) of BAHF and 1.24 g (0.0050 mol; of structural units derived from all amines and their derivatives) were added to a three-necked flask. 4.5 mol% relative to the structural unit), 2.18 g (0.020 mol; 18.2 mol% relative to the structural units derived from all amines and their derivatives) of MAP as an end cap agent, and 150.00 g of NMP were weighed and dissolved. Here, a solution of 31.02 g (0.10 mol; 100 mol% of structural units derived from all carboxylic acids and their derivatives) of ODPA dissolved in 50.00 g of NMP was added, stirred at 20°C for 1 hour, and then stirred at 50°C. and stirred for 4 hours. After that, 15 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotropically mixing water with xylene. After completion of the reaction, the reaction solution was added to 3 L of water, and the precipitated solid was filtered. The obtained solid was washed with water three times and then dried in a vacuum dryer at 80°C for 24 hours to obtain polyimide resin (PI-1). The weight average molecular weight (Mw) of the obtained polyimide resin (PI-1) was 27,000 and the acid equivalent was 350.

<Synthesis Example 2 Synthesis of HA>

In a three-necked flask, 18.31 g (0.05 mol) of BAHF, 17.42 g (0.3 mol) of propylene oxide, and 100 mL of acetone were weighed and dissolved. Here, a solution of 20.41 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 10 mL of acetone was added dropwise. After the dropwise addition was completed, the reaction was performed at -15°C for 4 hours and then returned to room temperature. The precipitated white solid was collected by filtration and dried under vacuum at 50°C. 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of 2-methoxyethanol, and 2 g of 5% palladium carbon was added. Hydrogen was introduced using a balloon and reacted at room temperature for 2 hours. After 2 hours, it was confirmed that the balloon was no longer deflated. After completion of the reaction, the catalyst palladium compound was removed by filtration, distilled off under reduced pressure, and concentrated to obtain a hydroxy group-containing diamine compound (HA) having the following structure.

<Synthesis Example 3 Synthesis of polyimide precursor resin (PIP-1)>

Under a dry nitrogen stream, 44.42 g (0.10 mol; 100 mol% of structural units derived from all carboxylic acids and their derivatives) of 6FDA and 150 g of NMP were weighed and dissolved in a three-necked flask. Here, in 50 g of NMP, 14.65 g (0.040 mol; 32.0 mol% of the structural units derived from all amines and their derivatives) and 18.14 g (0.030 mol; of structural units derived from all amines and their derivatives) of HA. A solution containing 24.0 mol%) and 1.24 g (0.0050 mol; 4.0 mol% relative to structural units derived from all amines and their derivatives) of SiDA was added, stirred at 20°C for 1 hour, and then stirred at 50°C for 2 hours. Stirred. Next, as an end capping agent, a solution of 5.46 g (0.050 mol; 40.0 mol% of structural units derived from all amines and their derivatives) of MAP dissolved in 15 g of NMP was added, and stirred at 50°C for 2 hours. After that, a solution of 23.83 g (0.20 mol) of DFA dissolved in 15 g of NMP was added. After completion of the addition, it was stirred at 50°C for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction solution was added to 3 L of water, and the precipitated solid was filtered. After washing the obtained solid three times with water, it was dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide precursor resin (PIP-1). The weight average molecular weight (Mw) of the obtained polyimide precursor resin (PIP-1) was 20,000 and the acid equivalent was 450.

<Synthesis Example 4 Synthesis of polyimide precursor resin (PIP-2)>

Under a dry nitrogen stream, 21.2 g (0.035 mol) of HA, 7.0 g (0.035 mol) of DAE, and 1.2 g (0.005 mol) of SiDA obtained in Synthesis Example 2 were dissolved in 400 g of NMP. Here, 31.0 g (0.10 mol) of ODPA was added along with 50 g of NMP, and stirred at 40°C for 1 hour. After that, 5.5 g (0.050 mol) of MAP was added and stirred at 40°C for 1 hour. Additionally, a solution of 8.3 g (0.07 mol) of DFA dissolved in 10 g of NMP was added. After the addition was completed, it was stirred at 40°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature and then added to 3L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain an alkali-soluble resin (PIP-2) made of a polyimide precursor resin with an acid equivalent of 275 g/mol.

<Synthesis Example 5 Synthesis of polyimide precursor resin (PIP-3)>

In the same manner as in Synthesis Example 4, an alkali-soluble resin (PIP-3) consisting of a polyimide precursor resin with an acid equivalent of 329 g/mol was obtained by adjusting the amount of DFA charged to 13.1 g (0.11 mol).

<Synthesis Example 6 Synthesis of polyimide precursor resin (PIP-4)>

In the same manner as in Synthesis Example 4, an alkali-soluble resin (PIP-4) consisting of a polyimide precursor resin with an acid equivalent weight of 366 g/mol was obtained by adjusting the amount of DFA charged to 16.7 g (0.14 mol).

<Synthesis Example 7 Synthesis of polybenzoxazole resin (PBO-1)>

In a 500 mL round-bottomed flask equipped with a Dean-Stark water separator and cooling tube containing toluene, 34.79 g (0.095 mol; 95.0 mol% of structural units derived from all amines and their derivatives) of BAHF and 1.24 g (0.0050 mol) of SiDA. mol; 5.0 mol% relative to the structural units derived from all amines and their derivatives), 75.00 g of NMP was weighed and dissolved. Here, 19.06 g (0.080 mol; 66.7 mol% of structural units derived from total carboxylic acids and their derivatives) of BFE to 25.00 g of NMP, and 6.57 g (0.040 mol; total carboxylic acids) of NA as an end capping agent. and the structural unit derived from its derivative (33.3 mol%) was added and stirred at 20°C for 1 hour, followed by stirring at 50°C for 1 hour. After that, the mixture was heated and stirred at 200°C or higher for 10 hours under a nitrogen atmosphere to perform a dehydration reaction. After completion of the reaction, the reaction solution was added to 3 L of water, and the precipitated solid was filtered. After washing the obtained solid three times with water, it was dried in a vacuum dryer at 80°C for 24 hours to obtain polybenzoxazole resin (PBO-1). The weight average molecular weight (Mw) of the obtained polybenzoxazole resin (PBO-1) was 25,000, and the acid equivalent was 330.

<Synthesis Example 8 Synthesis of polybenzoxazole precursor resin (PBOP-1)>

In a 500 mL round-bottomed flask equipped with a Dean-Stark water separator and cooling tube containing toluene, 34.79 g (0.095 mol; 95.0 mol% of structural units derived from all amines and their derivatives) of BAHF and 1.24 g (0.0050 mol) of SiDA. mol; 5.0 mol% relative to the structural units derived from all amines and their derivatives), 70.00 g of NMP was weighed and dissolved. Here, a solution of 19.06 g (0.080 mol; 66.7 mol% of structural units derived from total carboxylic acids and their derivatives) of BFE dissolved in 20.00 g of NMP was added, stirred at 20°C for 1 hour, and then stirred at 50°C. and stirred for 2 hours.

Next, as an end capping agent, a solution of 6.57 g (0.040 mol; 33.3 mol% based on structural units derived from all carboxylic acids and their derivatives) of NA dissolved in 10 g of NMP was added, and stirred at 50°C for 2 hours. After that, it was stirred at 100°C for 2 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was added to 3 L of water, and the precipitated solid was filtered. After washing the obtained solid three times with water, it was dried in a vacuum dryer at 80°C for 24 hours to obtain polybenzoxazole precursor resin (PBOP-1). The weight average molecular weight (Mw) of the obtained polybenzoxazole precursor resin (PBOP-1) was 20,000 and the acid equivalent was 330.

<Synthesis Example 9 Synthesis of polysiloxane resin solution (PS-1)>

23.84 g (35 mol%) of MeTMS, 49.57 g (50 mol%) of PhTMS, 3.81 g (5 mol%) of TMOS, and 76.36 g of PGMEA were injected into the three-necked flask. Air was flowed into the flask at 0.05 L/min, and the mixed solution was heated to 40°C in an oil bath while stirring. While further stirring the mixed solution, an aqueous phosphoric acid solution containing 0.271 g of phosphoric acid dissolved in 28.38 g of water was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was stirred at 40°C for 30 minutes to hydrolyze the silane compound. After completion of hydrolysis, a solution of 13.12 g (10 mol%) of TMSSucA dissolved in 8.48 g of PGMEA was added. After that, the bath temperature was set to 70°C and stirred for 1 hour, and then the bath temperature was continuously raised to 115°C. After the start of the temperature increase, the internal temperature of the solution reached 100°C about 1 hour later, and the solution was heated and stirred for 2 hours (internal temperature was 100 to 110°C). After heating and stirring the resulting resin solution for 2 hours and cooling it in an ice bath, 2% by weight of anion exchange resin and cation exchange resin were added to the resin solution, respectively, and stirred for 12 hours. After stirring, the anion exchange resin and cation exchange resin were removed by filtration to obtain a polysiloxane resin solution (PS-1). The weight average molecular weight (Mw) of the obtained polysiloxane resin was 4,200, and the carboxylic acid equivalent (acid equivalent) was 700 g/mol.

<Synthesis Example 10 Synthesis of photosensitizer (quinonediazide compound b-1)>

Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazidesulfonilic acid chloride were mixed with 1,4-di. It was dissolved in 450 g of oxalic acid and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not exceed 35°C. After dropping, it was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. Afterwards, the precipitate that precipitated was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a photosensitizer (quinonediazide compound b-1) with the following structure.

<Preparation of salt-forming compound d-1>

9.25 g (0.018 mol) of C.I. Basic Blue 7 and 200 g of pure water as a basic dye were added to the separable flask, and stirred at 60°C for 30 minutes. As an acid dye, an aqueous solution in which 11.50 g (0.019.8 mol) of C.I. Acid Red 52 was dissolved in 120 g of pure water was added and stirred at 60°C for 60 minutes. After that, heating was stopped and the mixture was stirred and cooled to room temperature. After cooling to room temperature, the reaction solution was filtered to obtain a purple solid. This solid was dried at 60°C under reduced pressure for 8 hours to obtain salt-forming compound d-1.

<Preparation of salt-forming compound d-2>

In the same manner as d-1, salt-forming compound d-2 was obtained using C.I. Basic Blue 26 instead of C.I. Basic Blue 7 as a basic dye.

<Preparation of pigment dispersion 1>

After adding 15.00 g of S-20000, a pigment dispersant having a basic group, to 742.39 g of PGMEA as a solvent component, 2.70 g of a PGMEA solution containing 1.00% by weight of 4-methylbenzenesulfonic acid was added. Next, after stirring for 1 hour at atmospheric pressure/liquid temperature of 25°C, the mixture was allowed to stand for an additional 6 hours to form a salt in advance of the basic group of S-20000 and the sulfo group of 4-methylbenzenesulfonic acid. Additionally, 149.91 g of alkali-soluble resin solution (resin solution obtained by dissolving PIP-1 using PGMEA to a solid content of 30% by weight (solid content 30.0% by weight)) was added, and after stirring for 30 minutes, 90.00 g of the following was added. The benzodifuranone-based black pigment represented by the structure was mixed and stirred for 20 minutes to obtain a preliminary dispersion. The preliminary dispersion liquid is fed into a bead mill filled with 75% by volume of 0.4 mmϕ zirconia beads ("TORAYCERAM" (registered trademark), manufactured by Toray Industries, Inc.) as a dispersion medium, and dispersion treatment is performed once, followed by a circulation method. Wet media dispersion treatment was performed. After 30 minutes, every 10 minutes of dispersion treatment time, an appropriate amount is extracted from the discharge port of the disperser into the glass bottle container, and the sampled pigment dispersion is subjected to a laser diffraction/scattering method particle size distribution measuring device (UPA150, manufactured by Microtrac Retsch GmbH). was set to measure the average dispersed particle diameter. The average dispersed particle diameter at 30 minutes after sampling is 150 ± 10 nm as media diameter D50 (cumulative 50% volume average diameter), and 300 ± 30 nm as media diameter D90 (cumulative 90% volume average diameter). The pigment dispersion liquid that fell within the range was designated as “pigment dispersion liquid 1.”

<Preparation of pigment dispersion 2>

In the same procedure as in “Pigment Dispersion 1,” the dissolution of PIP-1 was changed to PGMEA, and “Pigment Dispersion 2” was prepared using MBA.

<Preparation of pigment dispersion 3>

200 g of zirconium nitride particles (ZrN, manufactured by NISSHIN ENGINEERING INC.) manufactured by the thermal plasma method, 50 g of polyimide precursor resin (PIP-1), and 1000 g of γ-butyrolactone (GBL) were injected into the tank and mixed with a homomixer. The mixture was stirred for 20 minutes to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a disperser (ULTRA APEX MILL, manufactured by Hiroshima Metal & Machinery Co., Ltd.) equipped with a centrifugal separator filled with 75% by volume of 0.05 mmϕ zirconia beads, and incubated at a rotation speed of 10 m/s for 3 hours. Dispersion was performed to obtain pigment dispersion 3 with a solid content concentration of 20% by weight and a colorant/resin (weight ratio) = 80/20. The composition is shown in Table 1.

<Preparation of pigment dispersion 4>

In the same manner as pigment dispersion 3, pigment dispersion 4 was obtained by changing the alkali-soluble resin to be added to PIP-2.

<Preparation of pigment dispersion 5>

In the same manner as pigment dispersion 3, pigment dispersion 5 was obtained by changing the alkali-soluble resin to be added to PIP-3.

<Preparation of pigment dispersion 6>

In the same manner as pigment dispersion 3, pigment dispersion 6 was obtained by changing the alkali-soluble resin to be added to PIP-4.

<Preparation of pigment dispersion 7>

30.00 g of Pigment Dispersant 1 was added to 770.00 g of PGMEA as a solvent, and after stirring for 5 minutes, 100.00 g of ZCR-1569H was added and stirred for 30 minutes. Additionally, after adding 100.00 g of S0100CF as component (b), it was stirred for 30 minutes to obtain a preliminary stirred solution. A vertical vessel filled with pulverizing media (zirconium oxide: hafnium oxide: yttrium oxide: aluminum oxide = weight ratio 93.3:1.5:4.9:0.3, manufactured by Toray Industries, Inc.) made of a complex oxide of 0.4 mmϕ at a filling rate of 75% by volume. The preliminary stirring liquid was sent to the bead mill, and the first wet media dispersion treatment was performed in a circular manner at a circumferential speed of 8 m/s for 3 hours. In addition, pulverizing media (zirconium oxide: hafnium oxide: yttrium oxide: aluminum oxide = weight ratio 93.3:1.5:4.9:0.3, manufactured by Toray Industries, Inc.) made of a complex oxide of 0.05 mmϕ was filled into the vessel at a filling rate of 75% by volume. The liquid was sent to a vertical bead mill, and a second wet media dispersion treatment was performed in a circular manner at a circumferential speed of 9 m/s for 6 hours, followed by filtration through a filter with a diameter of 0.8 μm to prepare Pigment Dispersion 1 with a solid content of 20.00% by weight. The combined weight of each raw material is shown in Table 2.

<Preparation of photosensitive resin composition R-1>

Polyimide precursor resin PI-1 obtained in Synthesis Example 1 as (A) alkali-soluble resin in (C) solvent of γ-butyrolactone (GBL) and ethyl lactate (EL) at a weight ratio of 1:1 under yellow light. , (B) Compound b-1 obtained in Synthesis Example 10 as a photosensitizer, (D) Compound d-1 as a salt-forming compound consisting of an acidic dye and a basic dye among the coloring materials, C.I. Solvent Blue 45 as a nonionic dye d-3, Thermochromic compound f-1 (BIP-PHBZ) represented by the following structure, other additives include heat crosslinking agent g-1 (HMOM-TPHAP), compound h-1 (bisphenol AF) having a phenolic hydroxyl group, and adhesion improving agent i- 1 (KBM-403) was added in the amount shown in Table 3 and stirred to dissolve, thereby preparing positive photosensitive resin composition R-1.

<Preparation of photosensitive resin compositions R-2 to R-6>

Similar to the preparation of R-1, R-2 to 6 were prepared according to the compositions shown in Table 3.

<Preparation of photosensitive resin composition R-7>

Under yellow light, 0.20 g of NCI-831, a photosensitizer, was added to 13.01 g of PGMEA and stirred for 3 minutes to dissolve. To this, 4.28 g of alkali-soluble polyimide resin solution A (a resin solution obtained by dissolving PI-1 using PGMEA so that the solid content is 30% by weight), and 1.02 g of alkali-soluble Cardo resin solution A (amine value 0 (mgKOH) /g), the resin acid value is 90 (mgKOH/g), the solid content is 44.2% by weight, and "ADEKA ARKLS" (registered trademark) WR-301 (ADEKA) is a PGMEA solution of alkali-soluble Cardo resin having a carboxyl group as an alkali-soluble group. (manufactured by CORPORATION) was added, and 0.99 g of DPCA-60, a compound having two or more radical polymerizable groups, was added and stirred to obtain a preparation solution. This mixture and 10.50 g of pigment dispersion liquid 1 sampled from the supernatant in a glass bottle were mixed and stirred for 30 minutes to obtain negative photosensitive resin composition R-7. The mixing amounts of raw materials are shown in Table 4.

<Preparation of photosensitive resin composition R-8>

Instead of alkali-soluble polyimide resin solution A, alkali-soluble polyimide resin solution B (a resin solution obtained by dissolving PI-1 using MBA so that the solid content is 30% by weight) was used, and instead of pigment dispersion 1, pigment dispersion 2 was used. Using the same procedure as R-7, negative photosensitive resin composition R-8 was prepared. The mixing amounts of raw materials are shown in Table 4.

<Synthesis Example 11 Synthesis of liquid-repellent materials (e-1) and (e-2)>

100 parts by weight of cyclohexanone was added to a 1000 mL reaction vessel equipped with a stirring device, a reflux cooling tube, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the temperature was raised to 110°C in a nitrogen gas atmosphere. The temperature of cyclohexanone was maintained at 110°C, and the monomer mixed solution shown in Table 5 was added dropwise at a constant rate over 2 hours using a dropping funnel to prepare each monomer solution. After the dropwise addition was completed, the monomer solution was heated to 115°C and reacted for 2 hours to obtain liquid-repellent materials (e-1) and (e-2).

<Synthesis Example 12 Synthesis of phenol resin (j-1)>

Under a dry nitrogen stream, 108.0 g (1.00 mol) of m-cresol, 75.5 g (0.93 mol of formaldehyde) of 37% by weight formaldehyde solution, 0.63 g (0.005 mol of formaldehyde) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were injected into the oil bath. It was immersed in the solution and a polycondensation reaction was performed for 4 hours while refluxing the reaction solution. After that, the temperature of the oil bath was raised over 3 hours, and then the pressure in the flask was reduced to 4.0 kPa to 6.7 kPa, volatile matter was removed, and the dissolved resin was cooled to room temperature to form a novolak-type phenol resin (j- 1) was obtained. The weight average molecular weight from GPC was 3,500.

<Preparation of photosensitive resin compositions R-9 and R-10>

Under the yellow light, each component was mixed in the mixing ratio shown in Table 6 and stirred sufficiently at room temperature to dissolve. Thereafter, the obtained solution was filtered through a filter with a pore diameter of 1 μm to obtain positive photosensitive resin compositions R-9 and R-10.

<Preparation of photosensitive resin composition R-11>

In 93.8 g of pigment dispersion 3, 50.5 g of alkali-soluble resin (PIP-1), 17.0 g of quinonediazide compound (b-1) as a photoacid generator, 13.6 g of phenol compound (h-1, bisphenol AF), Positive type photosensitive resin composition R-11 with a total solid concentration of 10% by weight and pigment/resin (weight ratio) = 15/85 was prepared by adding 0.2g of silicone surfactant (BYK-333), 105.0g of GBL, and 720.0g of PGME. got it The composition is shown in Table 7.

<Preparation of photosensitive resin composition R-12>

In the same manner as R-11, pigment dispersion 3 was replaced with pigment dispersion 4 as the pigment dispersion, and PIP-1 was replaced with PIP-2 as the alkali-soluble resin, thereby obtaining positive photosensitive resin composition R-12. The composition is shown in Table 7.

<Preparation of photosensitive resin composition R-13>

In the same manner as R-11, pigment dispersion 3 was replaced with pigment dispersion 5 as the pigment dispersion to be added, and PIP-1 was replaced with PIP-3 as the alkali-soluble resin, thereby obtaining positive photosensitive resin composition R-13. The composition is shown in Table 7.

<Preparation of photosensitive resin composition R-14>

In the same manner as R-11, pigment dispersion 3 was replaced with pigment dispersion 6 as the pigment dispersion, and PIP-1 was replaced with PIP-4 as the alkali-soluble resin, thereby obtaining positive photosensitive resin composition R-14. The composition is shown in Table 7.

<Preparation of photosensitive resin composition R-15>

Yellow light, (A) polyimide precursor resin (PIP-1) (10.0g) as an alkali-soluble resin, (B) f-1 (1.2g) as a photosensitizer, and (C) PGME (32.0g) as an organic solvent. Added to GBL (8.0 g). Thereafter, the obtained solution was filtered through a 0.45 μm phi filter to obtain positive photosensitive resin composition R-15.

<Preparation of photosensitive resin composition R-16>

Under a yellow light, 0.38 g of OXE03 as a photopolymerization initiator was added to a mixed solvent of 8.50 g of MBA and 16.16 g of PGMEA and stirred for 10 minutes to dissolve. There, 1.88 g of MEK-ST-40 as component (a), which is a silica particle dispersion, was added and stirred for 10 minutes to dissolve. Next, 4.61 g of ZAH-106, 0.45 g of TR4020G, 0.38 g of DPCA-60, and 0.97 g of GA-5060P were added and stirred for 30 minutes to obtain a transparent mixture. 16.69 g of pigment dispersion liquid 7 was mixed with this mixture and stirred for 30 minutes to prepare negative photosensitive resin composition R-16 with a solid content of 15.00% by weight. The combined weight of each raw material is shown in Table 8.

<Preparation of photosensitive resin composition R-17>

As in the preparation of R-16, negative photosensitive resin composition R-17 was prepared using OSCAL-1421 instead of MEK-ST-40 in the mixing ratio shown in Table 8. The combined weight of each raw material is shown in Table 8.

<Preparation of photosensitive resin composition R-18>

As in the preparation of R-16, negative photosensitive resin composition R-18 was prepared using MEK-ST-L instead of MEK-ST-40 and in the mixing ratio shown in Table 8. The combined weight of each raw material is shown in Table 8.

<Examples 1 to 25, Comparative Examples 1 to 3>

The surface roughness of the pixel division layer and the spacer, the diffused reflected light of the substrate, the adhesion to the organic EL display device, weather resistance reliability, electrical reliability, and luminescence characteristics of each Example and Comparative Example were evaluated as follows.

First, AgPdCu (100 nm) and crystalline ITO (10 nm) were sequentially deposited as first electrodes on the center part of a 100 mm × 100 mm PET substrate using a vacuum sputtering method, with a line width of 60 μm, a pitch of 100 μm, and a length of 10 mm. , etched in 100 stripes. That is, the exposed portion of the substrate is 40 μm wide. Here, the photosensitive resin composition based on each example and comparative example shown in Table 9 was applied by spin coating, and then prebaked for 2 minutes on a hot plate at 100°C to form a film.

This film was exposed to UV through the halftone photomask shown in Table 9, then developed with a 2.38% TMAH aqueous solution. If it was a negative type, only the unexposed portion was dissolved, if it was a positive type, only the exposed portion was dissolved, and then rinsed with pure water to form a pattern. got it After that, it was cured in an oven at 250°C in a nitrogen atmosphere for 60 minutes to obtain a substrate with a pixel division layer and a spacer pattern. Additionally, by adjusting the rotation speed in the spin coating method, the film thickness of the pixel dividing layer was set to 1.5 um and the film thickness of the spacer was set to 1.5 um in all examples and comparative examples.

Additionally, in Comparative Example 1, the pixel division layer and the spacer were manufactured separately using a photomask generally called a Fullton mask without a semi-transparent portion. In other words, the pixel division layer is applied, pre-baked, exposed, developed, and cured, and then the spacer is applied, pre-baked, exposed, developed, and cured. Additionally, in Comparative Example 3, after curing, a roughening treatment was performed using a plasma processing device (SPC-100B+H, manufactured by Hitachi High-Tech Corporation) in RIE mode, oxygen gas, 1000 W, and 60 seconds.

Table 10 shows the results of evaluating the surface roughness of the pixel division layer, the spacer, and the diffuse reflected light of the substrate in this state.

Next, an organic EL layer was formed on the entire surface of the substrate with this pattern by vacuum deposition. Additionally, the degree of vacuum during deposition was set to 1×10 ^-3 Pa or less, and the substrate was rotated with respect to the deposition source during deposition. First, 10 nm of compound (HT-1) was deposited as a hole injection layer, and 50 nm of compound (HT-2) was deposited as a hole transport layer. Next, as the light emitting layer, a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were deposited to a thickness of 40 nm with a dope concentration of 10% by volume. Next, as an electron transport layer, compound (ET-1) and LiQ were laminated at a volume ratio of 1:1 and a thickness of 40 nm. The hole injection layer, hole transport layer, light emitting layer, and electron transport layer up to this point are called the first light emitting unit.

After that, 2 nm of LiQ was deposited as an electron injection layer. The structure of the compound used as the organic EL layer is shown below.

Additionally, a 10 nm stripe-shaped second electrode with a line width of 400 μm, a 500 μm pitch, and a length of 10 mm was deposited to intersect the first electrode with 10 nm of Mg and Ag at a volume ratio of 10:1. In addition, the film thickness mentioned here is the value displayed by a crystal oscillation type film thickness monitor.

In this way, an organic EL display device having 100 first electrodes, 20 second electrodes, and 200 light-emitting elements where they intersect was completed. Figure 8 shows a schematic diagram of the organic EL display device of this embodiment, and Figure 9 shows a schematic diagram of the light emitting element omitting the organic EL layer. After that, the adhesion, weather resistance reliability, and electrical reliability of the organic EL display device were evaluated. The results are shown in Table 10.

(Table 9-1)

(Table 9-2)

(Table 10-1)

(Table 10-2)

<Example 26>

In the first light emitting unit, an organic EL display device was manufactured in the same manner as in Example 1 except that LiQ was not used in the electron transport layer and only a compound (ET-1) was used, and the adhesion, weathering reliability, electrical reliability, and light emission of the organic EL display device were tested. characteristics were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

<Example 27>

In the first light emitting unit, an organic EL display device was manufactured in the same manner as in Example 1 except that LiQ was not used in the electron transport layer and only a compound (ET-2) was used, and the adhesion, weathering reliability, electrical reliability, and light emission of the organic EL display device were tested. characteristics were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

<Example 28>

In the first light emitting unit, an organic EL display device was manufactured in the same manner as in Example 1 except that LiQ was not used in the electron transport layer and only a compound (ET-3) was used, and the adhesion, weathering reliability, electrical reliability, and light emission of the organic EL display device were tested. characteristics were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

<Example 29>

In the first light emitting unit, an organic EL display device was manufactured in the same manner as in Example 1 except that LiQ was not used in the electron transport layer and only a compound (ET-4) was used, and the adhesion, weathering reliability, electrical reliability, and light emission of the organic EL display device were tested. characteristics were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

<Example 30>

Similarly to Example 1, after obtaining a substrate with a pattern, the first light emitting unit was laminated as an organic EL layer. Thereafter, on the first light emitting unit, compound (ET-1) as an n-type charge generation layer and metal Li as a dopant material were deposited at 10 nm so that the deposition rate ratio was compound (ET-1):Li = 99:1. Then, 10 nm of compound (HT-1) was deposited as a p-type charge generation layer.

Continuing with the charge generation layer, an organic EL layer similar to that of the first light emitting unit was formed again and made into a tandem type. After that, 2 nm of LiQ was deposited as an electron injection layer. Additionally, a 10 nm stripe-shaped second electrode with a line width of 400 μm, a 500 μm pitch, and a length of 10 mm was deposited to intersect the first electrode with 10 nm of Mg and Ag at a volume ratio of 10:1. In addition, the film thickness mentioned here is the value displayed by a crystal oscillation type film thickness monitor.

In this way, an organic EL display device having 100 first electrodes, 20 second electrodes, and 200 light-emitting elements where they intersect was completed. After that, the adhesion, weathering reliability, electrical reliability, and luminescence characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

<Example 31>

An organic EL display device was manufactured in the same manner as in Example 30 except that compound (ET-1) was replaced with compound (ET-2) in the n-type charge generation layer, and the adhesion, weather resistance reliability, electrical reliability, and light emission of the organic EL display device were tested. characteristics were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

<Example 32>

An organic EL display device was manufactured in the same manner as in Example 30 except that compound (ET-1) was replaced with compound (ET-3) in the n-type charge generation layer, and the adhesion, weather resistance reliability, electrical reliability, and light emission of the organic EL display device were tested. characteristics were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

<Example 33>

An organic EL display device was manufactured in the same manner as in Example 30 except that compound (ET-1) was replaced with compound (ET-4) in the n-type charge generation layer, and the adhesion, weather resistance reliability, electrical reliability, and light emission of the organic EL display device were tested. characteristics were evaluated. The conditions of the photosensitive resin composition and photomask are shown in Table 9, and the evaluation results are shown in Table 10.

1: Substrate 2: First electrode
3: Pixel division layer 4: Spacer
5: Organic EL layer 6: Second electrode
7: TFT 8: Planarization layer
9: sealing layer 10: polarizing layer
11: ultraviolet absorbing layer 12: light transmitting portion
13: semi-transparent part 14: light-shielding part
15: Cylinder 16: Measurement target range of Ra1
17: Ra2 measurement target range 18: Organic EL display device
19: light emitting element

Claims (18)

An organic EL display device having a substrate having a first electrode, a pixel split layer, and a spacer on a substrate, and also an organic EL layer and a second electrode, wherein the surface roughness (Ra1) of the pixel split layer and the surface roughness (Ra2) of the spacer are ) An organic EL display device in which Ramax is 1.0 nm or more and 50 nm or less, when the maximum value is Ramax. According to claim 1,
An organic EL display device in which Ra1 is Ramax. According to claim 2,
An organic EL display device, wherein the area of the interface between the pixel division layer and the organic EL layer is 50% or more of the area of the interface between the substrate and the organic EL layer. According to claim 1,
An organic EL display device in which Ra2 is Ramax. According to claim 4,
An organic EL display device in which the area of the interface between the spacer and the organic EL layer is 50% or more of the area of the interface between the substrate and the organic EL layer. The method according to any one of claims 1 to 5,
An organic EL display device in which the absolute value of the difference between Ra1 and Ra2 is 1.0 nm or more. The method according to any one of claims 1 to 6,
An organic EL display device in which the pixel split layer contains silica particles with a primary particle diameter of 5 to 30 nm. The method according to any one of claims 1 to 7,
An organic EL display device wherein the pixel split layer includes a cured film of a photosensitive resin composition containing an alkali-soluble resin. According to claim 8,
The alkali-soluble resin is at least one selected from the group consisting of acrylic resin, phenol resin, polysiloxane resin, cardo resin, polyimide resin, polyimide precursor resin, polybenzoxazole resin, and polybenzoxazole precursor resin. An organic EL display device containing According to claim 8 or 9,
An organic EL display device wherein the photosensitive resin composition contains a coloring material. The method according to any one of claims 8 to 10,
An organic EL display device in which the photosensitive resin composition contains a liquid-repellent material. The method according to any one of claims 1 to 11,
An organic EL display device wherein the organic EL layer includes an electron transport layer and/or a charge generation layer. According to claim 12,
An organic EL display device wherein the electron transport layer and/or the charge generation layer include a donor dopant. According to claim 13,
An organic EL display device wherein the donor dopant contains at least one member selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, inorganic salts of the above metals, and complexes of the above metals and organic substances. The method according to any one of claims 12 to 14,
An organic EL display device wherein the electron transport layer and/or the charge generation layer include a compound having a phenanthroline skeleton represented by the following general formula (1).

(Here, R ₁ to R ₈ may be the same or different, and are selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, and a heterocyclic group. However, R ₁ At least one of R ₃ , R ₆ , and R ₈ is selected from adamantyl group, norbornyl group, phenylvinyl group, β-naphthyl group, phenanthrene group, and pyrenyl group.) The method according to any one of claims 12 to 14,
An organic EL display device wherein the electron transport layer and/or the charge generation layer include a compound having a phenanthroline skeleton represented by the following general formula (2).

(Here, R ₉ to R ₁₆ may be the same or different, and are selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, a _{heterocyclic group} , and At least one _of R ₉ to R ₁₆ is X _1. n represents a natural number from 2 to 6. It is a linking unit that connects a plurality of n-valent phenanthroline skeletons derived from any one of hexane, spirobifluorene, triphenylamine, tryptycene, and structures formed by combining them.) A method of manufacturing an organic EL display device having a substrate having a first electrode, a pixel split layer, and a spacer on a substrate, and also having an organic EL layer and a second electrode, comprising a step of batch processing the pixel split layer and the spacer, and batch processing the pixel split layer and the spacer. A method of manufacturing an organic EL display device, wherein the photomask is a halftone photomask having a light transmitting portion, a light blocking portion, and a semi-transmissive portion. According to claim 17,
A method of manufacturing an organic EL display device, wherein the semi-transmissive portion has a transmittance of 15 to 50% of the transmittance of the light transmitting portion.