KR20240088697A - Organic EL display device - Google Patents

Abstract

The present invention provides an organic EL display device having high light-shielding properties and a pixel dividing layer having a narrow aperture width, and having high light emission reliability.
The present invention is an organic EL display device comprising a substrate, a planarization layer, a first electrode, a pixel splitting layer, a light emitting pixel, and a second electrode in this order, wherein the pixel splitting layer includes a layer (A) and a layer (B). wherein the layer (A) is a layer disposed on the surface of the first electrode by partially exposing the surface of the first electrode, and the layer (B) is disposed on at least a portion of the surface of the layer (A) This layer (A) contains a cured product of the negative photosensitive composition (a) containing a pigment and/or dye, a compound having two or more ethylenically unsaturated double bond groups in the molecule, and a photopolymerization initiator, , an organic EL display device in which the layer (B) contains a cured product of a positive photosensitive composition (b) containing a resin and a photoacid generator.

Description

Organic EL display device

The present invention relates to organic EL display devices.

Many products equipped with organic electroluminescence (EL) display devices, such as smartphones, televisions, and in-vehicle monitors, are being developed. Recently, for the purpose of improving the visibility and contrast of organic EL display devices, the pixel dividing layer is blackened to suppress light mixing due to light leakage to adjacent light-emitting pixels and reflection of external light such as sunlight, thereby improving light blocking properties. The technology it provides is attracting attention. In addition, there is also a demand for high-definition display portions by reducing the size of the light-emitting pixels. Since each light-emitting pixel, such as red/green/blue, is formed in the opening of a pattern-shaped pixel division layer that functions as an insulating layer, in order to arrange a large number of small light-emitting pixels within the surface of the display unit, a plurality of openings with narrow aperture widths are required. It is necessary to form a pattern of the pixel division layer. The pixel split layer is usually formed by a photolithography method using a photosensitive composition, and as a photosensitive composition for forming a black pixel split layer, for example, a negative photosensitive composition containing an organic black pigment is disclosed in Patent Document 1. and an organic EL display device including a pixel division layer formed using the same is disclosed.

International Publication No. 2021/111860

However, when a pixel dividing layer having an aperture with a narrow aperture width is formed using the negative photosensitive composition disclosed in Patent Document 1, there is a problem in that high luminescence reliability cannot be obtained.

From the above, there has been a desire for an organic EL display device that has high light-shielding properties, has a pixel dividing layer with a narrow aperture, and has high light emission reliability.

The present invention is as follows.

(1) An organic EL display device comprising a substrate, a planarization layer, a first electrode, a pixel splitting layer, a light emitting pixel, and a second electrode in this order, wherein the pixel splitting layer includes a layer (A) and a layer (B). do,

The layer (A) is a layer disposed on the surface of the first electrode by partially exposing the surface of the first electrode, and the layer (B) is a layer disposed on at least a portion of the surface of the layer (A). ,

The layer (A) contains a cured product of the negative photosensitive composition (a) containing a pigment and/or dye, a compound having two or more ethylenically unsaturated double bond groups in the molecule, and a photopolymerization initiator, and the layer ( B) An organic EL display device containing a cured product of the positive photosensitive composition (b) containing this resin and a photoacid generator.

(2) In the display unit, the organic layer according to (1), wherein the layer (B) has a portion covering the surface of the layer (A) of 20 to 100% of 100% of the total surface area of the layer (A). EL display device.

(3) The organic EL display device according to (1) or (2), further comprising a color filter on the light extraction side of the light-emitting pixel.

(4) The organic EL display device according to any one of (1) to (3), wherein the layer (A) is a display portion and has an opening with an opening area of 30.0 to 260.0 μm ² where the light-emitting pixels are disposed.

(5) The organic EL display device according to any one of (1) to (4), wherein the cured product of the positive photosensitive composition (b) contains a resin having an imide bond and/or a benzoxazole skeleton.

(6) (1) wherein the cured product of the negative photosensitive composition (a) contains the pigment, and the pigment contains a benzodifuranone-based black pigment represented by formula (1) or formula (2) described later. The organic EL display device according to any one of to (5).

(7) The cured product of the negative photosensitive composition (a) is C. I. Pigment Red 123, C. I. Pigment Red 149, C. I. Pigment Red 178, C. I. Pigment Red 179, C. I. Pigment Red 190, and C. I. Pigment Violet 29. and the organic EL according to any one of (1) to (6), further comprising at least one perylene-based organic pigment selected from the group consisting of 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole. display device.

(8) The organic according to any one of (1) to (7), wherein the cured product of the negative photosensitive composition (a) further contains 3,4,9,10-perylenetetracarboxylic acid bisbenzoimidazole. EL display device.

(9) In the area where the layer (B) is disposed on the surface of the layer (A), the maximum value of the film thickness of the layer (A) is 0.5 to 3.0 μm, and the film thickness of the layer (B) is 0.5 to 3.0 μm. The organic EL display device according to any one of (1) to (8), wherein the maximum value of is 0.1 to 3.0 μm.

(10) The organic EL display device according to any one of (1) to (9), wherein the optical density (OD/μm) per 1 μm film thickness of the layer (A) is 0.5 to 1.5.

(11) (1) to (10), wherein the cured product of the negative photosensitive composition (a) contains silica particles having a primary particle diameter of 5 to 30 nm and an aspect ratio (major axis/minor axis) of 1.0 to 1.5. The organic EL display device according to any one of the above.

According to the present invention, an organic EL display device is provided that has high light-shielding properties, has a pixel dividing layer having a narrow aperture width, and has high luminescence reliability.

1 is a cross-sectional view of a TFT substrate in an organic EL display device that can be cited as a specific example of an embodiment of the present invention.
Fig. 2 is a cross-sectional view of a color filter substrate that may be included in an organic EL display device as a specific example of the embodiment of the present invention.
Figure 3 shows a specific example of the embodiment of the present invention, where the layer (B) is arranged to cover the entire surface of the layer (A), and the layer (A) and layer (B) have the same opening width. A cross-sectional view of the pixel split layer formation substrate is shown.
FIG. 4 shows a cross-sectional view of a pixel division layer forming substrate having a spacer function and having the layer (B) disposed on a part of the surface of the layer (A), which can be cited as a specific example of the embodiment of the present invention.
Figure 5 shows a specific example of the embodiment of the present invention, in which the layer (B) is arranged to cover the entire surface of the layer (A), and the layer (A) and layer (B) have the same opening width. , shows a cross-sectional view of a pixel division layer forming substrate having a spacer function.
Figure 6 shows a specific example of the embodiment of the present invention, in which the layer (B) is arranged to cover the entire surface of the layer (A), and the layer (A) and layer (B) have the same opening width. , shows a cross-sectional view of a pixel division layer forming substrate having a spacer function.
Figure 7 is a specific example of the embodiment of the present invention, where the layer (B) covers the surface of the layer (A) other than the inclined portion located at the pattern peripheral edge of the opening of the layer (A). The layer (A) is a layer disposed on the surface of the first electrode and the surface of the planarization layer, and shows a cross-sectional view of the pixel split layer forming substrate having a spacer function.
FIG. 8 shows a layer (A) having hole pattern-shaped openings in which the opening area where the light-emitting pixels are arranged is within the range of 30.0 to 260.0 μm ² in the display portion, which can be cited as a specific example of the embodiment of the present invention. .
FIG. 9 shows a layer (A) having square pattern-shaped openings in which light-emitting pixels are disposed in a range of 30.0 to 260.0 μm ² in a display portion, which is a specific example of the embodiment of the present invention. .
Figure 10 shows an example of the layer (A), the light-emitting portion, and the non-light-emitting portion when observing the light-emitting pixel portion.
Figure 11 shows the manufacturing process of the organic EL display device, including the pixel split layer formation process, in all examples and comparative examples.

Hereinafter, the present invention will be described in detail. The numerical range expressed using “~” means a range that includes the numerical values written before and after “~” as the lower limit and upper limit. The pixel split layer refers to a pixel split layer included in an organic EL display device and does not include the black matrix of the liquid crystal display device. Visible light refers to light in the range of 380 nm to less than 780 nm, and near-ultraviolet ray refers to light in the range of 200 nm to less than 380 nm. Light-shielding refers to the function of lowering the intensity of transmitted light compared to the intensity of light incident in the direction perpendicular to the cured film, and light-shielding refers to the degree to which visible light is shielded. Photosensitive composition refers to a composition that has photosensitivity to near-ultraviolet rays. Weight average molecular weight (Mw) means a value analyzed by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a calibration curve using standard polystyrene. Solid content means the ratio (% by weight) of components excluding solvent and water in the photosensitive composition.

“C.” is used to name some colorants. "I." is an abbreviation for Color Index Generic Name. Based on the color index published by The Society of Dyers and Colourists, for colorants that have been registered in the color index, the Color Index Generic Name refers to the chemical structure of the pigment or dye or It represents the crystalline form.

As a result of verification of the above-described problem by the present inventors, a narrow aperture width can be achieved by using a negative photosensitive composition containing a pigment and/or dye, a compound having two or more ethylenically unsaturated double bond groups in the molecule, and a photopolymerization initiator. When an opening (for example, a square with a vertical width of 7.0 μm and a horizontal width of 7.0 μm) is formed, when an opening with a wide opening width is formed (for example, a square with a vertical width of 30.0 μm and a horizontal width of 30.0 μm) In comparison, it was found that the emission reliability of the finally obtained organic EL display device was inferior. That is, even if the same negative photosensitive composition is used, the smaller the light emitting pixel size determined from the aperture width of the aperture of the pixel dividing layer, the easier it is for the light emission reliability of the organic EL display device to decrease, making it difficult to achieve high definition of the display portion. So, I could see that there was a trade-off relationship.

In view of the above, the present inventors conducted intensive studies and came up with the idea of combining a layer containing a cured product of a negative photosensitive composition and a layer containing a cured product of a positive photosensitive composition, and the following configuration was adopted. In solving one problem, we found something that had a particularly remarkable effect.

That is, the present invention is an organic EL display device comprising a substrate, a planarization layer, a first electrode, a pixel splitting layer, a light emitting pixel, and a second electrode in this order, wherein the pixel splitting layer is comprised of layer (A) and layer (B). It includes, wherein the layer (A) is a layer disposed on the surface of the first electrode by partially exposing the surface of the first electrode, and the layer (B) is disposed on at least a portion of the surface of the layer (A) It is an arranged layer, wherein the layer (A) contains a cured product of the negative photosensitive composition (a) containing a pigment and/or dye, a compound having two or more ethylenically unsaturated double bond groups in the molecule, and a photopolymerization initiator. and the layer (B) is an organic EL display device containing a cured product of the positive photosensitive composition (b) containing a resin and a photoacid generator.

The organic EL display device of the present invention includes a substrate, a planarization layer, a first electrode, a pixel division layer, a light-emitting pixel, and a second electrode in this order.

Fig. 1 shows a cross-sectional view of a TFT substrate in an organic EL display device that can be cited as a specific example of an embodiment of the present invention.

Bottom gate type or top gate type TFTs 1 (thin film transistors) are installed in a matrix on the surface of the substrate 6, and cover the TFT 1 and the wiring 2 connected to the TFT 1. The TFT insulating layer 3 is formed in this state. Examples of the TFT 1 include oxide semiconductors such as In-Ga-Zn-O (IGZO) and Ga-Zn-Sn, and TFTs made of low-temperature polysilicon (LTPS). Additionally, a planarization layer 4 is formed on the surface of the TFT insulating layer 3, and a contact hole 7 for opening the wiring 2 is formed in the planarization layer 4. The contact hole 7 may have a circular opening, for example. The first electrode 5 is patterned on the surface of the planarization layer 4 and is connected to the wiring 2. The layer (A) 8 is disposed on the surface of the first electrode 5 by partially exposing the surface of the first electrode 5, and a portion of the surface of the layer (A) 8 is covered with the layer (B). (9) is arranged, and layer (A) (8) and layer (B) (9) form the pixel division layer (10). An opening is formed in the pixel split layer 10, and a light-emitting pixel 11 containing an organic EL light-emitting material is formed in the opening, and the second electrode 12 is formed in the layer (A) (8) and the layer (B). ) (9) and the light emitting pixel (11). The shape of the opening of the pixel division layer 10 is not particularly limited, and may be square, rectangular, circular, or elliptical, and the size of the light-emitting pixel 11 is determined by the layer (A) included in the pixel division layer 10 ( It is determined by the opening width of the opening in 8).

By sealing the TFT substrate with the above laminated structure under vacuum and then applying a voltage to the light-emitting pixel portion, it can be made to emit light as an organic EL display device.

The organic EL display device of the present invention may be a bottom emission type organic EL display device that extracts the light emitted from the light emitting pixel 11 to the substrate side through the substrate 6, and the light emitted through the second electrode 12. It may be a top emission type organic EL display device that extends to the opposite side of the substrate 6, and is not particularly limited.

If a hard plate-shaped substrate such as glass is used as the substrate 6, a rigid-type organic EL display device that cannot be bent can be obtained. As the glass, an alkali-free glass containing silicon as a main component and having an alkali metal element content of less than 0.5% can be preferably used. Among them, those with a small thermal expansion coefficient and excellent dimensional stability in high temperature processes of 250°C or higher are good, for example, OA-10G, OA-11 (all manufactured by Nippon Denki Glass Co., Ltd.), AN-100. (manufactured by Asahi Glass Co., Ltd.), and its thickness is usually 0.1 to 0.5 mm from the viewpoint of physical durability.

On the other hand, if a flexible substrate is used, a bendable flexible type organic EL display device can be obtained. As a flexible base material, a base material made of polyimide resin with high flexibility and excellent mechanical strength can be preferably used. As a method of manufacturing this, a solution containing polyamic acid is applied to the surface of a support and then heated to form polyimide resin. One example is a method of imidizing amidic acid to convert it into polyimide resin and then peeling the branched support with a laser or the like. Polyamic acid can be synthesized by reacting tetracarboxylic dianhydride and a diamine compound in an amide-based solvent such as N-methyl-2-pyrrolidone, and has a small thermal expansion coefficient and excellent dimensional stability, A polyamic acid having a residue of aromatic tetracarboxylic dianhydride and a residue of an aromatic diamine compound is preferred. Specific examples include polyamic acid having a residue of 3,3',4,4'-biphenyltetracarboxylic dianhydride and a residue of p-phenylenediamine. The thickness is usually 10 to 40 μm, and the substrate 6 can be made thinner compared to the case of using the alkali-free glass described above.

The planarization layer 4 is not particularly limited as long as it is a layer that functions as an insulating layer disposed as the base layer of the first electrode 5, and is formed to cover the convex portion based on the thickness of the TFT 1, and the first electrode (5) may be a layer that functions to form a pattern more smoothly. The planarization layer 4 can be patterned using, for example, the same photosensitive composition as the negative photosensitive composition (a) or positive photosensitive composition (b) described later, and the planarization layer 4 is a single layer or two layers. It may consist of the above.

The first electrode 5 may be made of any material as long as it is a film that functions as an anode electrode. As the first electrode 5, for example, a conductive metal oxide such as ITO (Indium Tin Oxide), ITZO (Indium Tin Zinc Oxide), IZO (Indium Zinc Oxide) can be used, and among these, it is excellent in transparency and conductivity. ITO can be preferably used. As a method of forming a pattern of ITO, first, ITO is deposited on the entire surface by sputtering, and then a positive resist material for etching is patterned by photolithography to obtain a resist pattern on the ITO film. Next, only the ITO film in the resist pattern non-forming area is removed with an etching liquid at a liquid temperature of 20 to 60°C, and then the resist pattern is removed with a resist stripping liquid at a liquid temperature of 20 to 60°C, and, if necessary, a desired crystallinity degree is obtained. A method of performing heat treatment as much as possible can be mentioned. ITO referred to here includes so-called amorphous ITO. As a positive resist material for etching, a positive photosensitive composition containing an alkali-soluble novolac resin can be used. As an etching solution, an aqueous solution containing nitric acid and hydrochloric acid or an aqueous oxalic acid solution can be used. Commercially available products include, for example, ITO-101N (manufactured by Kanto Chemical Co., Ltd.), "S-Clean" (registered trademark) IS-2, and IS-2. -3 (above, all manufactured by Sasaki Kagaku Yakuhin Co., Ltd.).

As a resist stripper, an organic amine-based aqueous solution can be used. Commercially available products include, for example, “Unlast” (registered trademark) M6, M6B, TN-1-5, and M71-2 (all from Junya Mitsukawa). Ku Keng Kyusho). When the organic EL display device of the present invention is a top emission type organic EL display device, in order to increase light extraction efficiency and improve luminance, the first electrode 5 is a laminated film in which a transparent conductive layer is laminated on the surface of a metal reflective layer. It is preferable, and for example, it may be a laminated structure of silver alloy/ITO or ITO/silver alloy/ITO. Examples of silver alloys include alloys of Ag and Cu, and alloys of Ag, Pd, and Cu.

The light emitting pixel 11 is not particularly limited, and the light emitted may have any peak wavelength. As the organic EL emitting material constituting the light emitting pixel 11, a material that combines a hole transport layer and/or an electron transport layer in addition to the light emitting layer can be preferably used. Examples of the light-emitting pixels of each color include red light-emitting pixels with a peak wavelength of 560 to 700 nm, blue light-emitting pixels with a peak wavelength of 420 to 490 nm, and green light-emitting pixels with a peak wavelength of 500 to 550 nm. The light-emitting pixel 11 may have a tandem light-emitting layer formed by stacking multiple types of light-emitting layers with different peak wavelengths. Examples of the tandem type light emitting layer include a white light emitting pixel formed by stacking a total of four light emitting layers of blue, yellow green, red, and blue in this order. A method of forming a pattern of the light emitting pixel 11 includes a mask deposition method. The mask deposition method is a method of depositing and patterning an organic compound using a deposition mask, and specifically, a method of performing vapor deposition by contacting a deposition mask having an opening with a desired pattern shape. Examples of a deposition mask that can be used to form the high-definition light-emitting pixel 11 include the deposition mask disclosed in Japanese Patent Application Laid-Open No. 2019-163543.

The second electrode 12 may be made of any material as long as it is a film that functions as a cathode electrode. As the second electrode 12, when the organic EL display device of the present invention is a top emission type organic EL display device, a layer made of an alloy of silver and magnesium is preferably used because light transmittance is high and light extraction efficiency is excellent. You can use it. It is preferable to form a thin film so that the layer has a high light transmittance in the visible region compared to the above-described first electrode 5. On the other hand, in the case of a bottom emission type organic EL display device, a layer made of aluminum alloy can be preferably used because light reflectivity is high and light extraction efficiency is excellent, and compared to the above-described first electrode 5, the visible region is improved. It is desirable to form a thick film so that the layer has a high light reflectance. The second electrode 12 can be formed by forming a film on the entire surface using a sputtering method.

The organic EL display device of the present invention may further include a color filter substrate consisting of at least one color filter and a substrate. Specifically, one example is a form in which a color filter substrate, the cross section of which is shown in FIG. 2, is bonded to the light extraction side of a TFT substrate in an organic EL display device, the cross section of which is shown in FIG. 1. By providing a color filter, light resistance to light in the near-ultraviolet to visible light region can be improved, and luminescence reliability can be improved, especially when used outdoors.

In addition, the light extraction side is the light emitting surface side of the organic EL display device. If the organic EL display device is a bottom emission type organic EL display device that extracts the light emitted from the light emitting pixel 11 to the substrate side through the substrate 6, the light extraction side is the substrate side. If the organic EL display device is a top emission type organic EL display device that extracts the emitted light to the opposite side of the substrate 6 through the second electrode 12, the light extraction side is the opposite side of the substrate 6.

That is, the organic EL display device of the present invention preferably further includes a color filter on the light extraction side of the light-emitting pixel.

A green color filter 15, a red color filter 16, and a blue color filter 17 are each patterned at the opening of the black matrix 14 disposed on the surface of the substrate 13. The opening width/shape of the opening of the black matrix 14 may be the same as or different from the opening width/shape of the opening of layer A in FIG. 1. The color filter substrate may be highly flexible, and can be easily bonded to the surface of the substrate 6 in FIG. 1 or the surface of the second electrode 12 using a thermosetting or near-ultraviolet curing transparent adhesive. Examples of the transparent adhesive include "Struck Bond" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.).

The pixel division layer 10 will be described in detail as follows.

The pixel division layer included in the organic EL display device of the present invention includes a layer (A) and a layer (B). The layer (A) is a layer disposed on the surface of the first electrode by partially exposing the surface of the first electrode, and the layer (B) is a layer disposed on at least a portion of the surface of the layer (A). . That is, the pixel division layer included in the organic EL display device of the present invention is a laminated film composed of a plurality of layers. If the layer (A) is a layer disposed on the surface of the first electrode by partially exposing the surface of the first electrode, the layer (A) may be a layer disposed only on the surface of the first electrode, or the layer (A) may be a layer disposed only on the surface of the first electrode. This means that in addition to the surface of the electrode, the layer may be disposed on the surface of another layer other than the first electrode. A specific example of a configuration in which the layer (A) has multiple types of underlying layers is preferably a configuration in which the layer (A) is a layer disposed on the surface of the first electrode and the surface of the planarization layer.

The configuration in which the layer (B) is disposed on at least part of the surface of the layer (A) has the effect of improving the light emission reliability of the organic EL display device. By laminating the layer (B) containing a cured product of the positive photosensitive composition (b) containing a resin and a photoacid generator, preferably high luminescence reliability can be obtained regardless of the resolution of the layer (A). there is.

High light emission reliability in this specification means that the area ratio of the light emitting part (pixel light emission area ratio) relative to the area of the light emitting pixel portion of the organic EL display device is maintained high, that is, the occurrence of non-light emitting parts due to pixel shrinkage is low. means that The higher the luminescence reliability, the longer the luminescence life, and the higher the value as a display device in that it can be used while maintaining high luminance over a long period of time. The area of the non-emission area, which tends to gradually progress from the peripheral edge of the light-emitting pixel portion toward the center, tends to increase easily as the size of the light-emitting pixel becomes smaller. Additionally, the smaller the light-emitting pixel size, the greater the change in the pixel light-emitting area ratio per 1.0 μm ² area of the non-light-emitting region.

A plurality of factors are considered to be the mechanism for exerting the technical effect of the present invention, but the layer (B) may be a compound having two or more ethylenically unsaturated double bond groups in the molecule remaining in the cured product of the negative photosensitive composition (a), It is thought that at least the effect of keeping unreacted components and/or decomposed products of the photopolymerization initiator inside the film of layer (A) and suppressing their emission into the light emitting device contributed.

The form of the pixel dividing layer in which the layer (B) is disposed on at least a portion of the surface of the layer (A) is not particularly limited, but specific examples of preferred embodiments in the organic EL display device of the present invention are shown in FIGS. 3 to 3. It is shown in 7. In the surface of the display portion of the organic EL display device, a plurality of these different types of pixel division layers may coexist. The display portion of an organic EL display device refers to an area on the light extraction side where light emitted from a light-emitting pixel is recognized by a user of the organic EL display device when the organic EL display device is driven. The content displayed by the display unit is not particularly limited, but examples include text information, images, or moving images. On the other hand, decorative parts such as bezel parts where light-emitting pixels are not arranged are not included in the display part.

The pixel division layer included in the organic EL display device of the present invention preferably has a step shape and a spacer function. By having a spacer function, when forming a light-emitting pixel, the contact area between the pixel division layer and the deposition mask can be reduced, defects and damage can be prevented, and production yield can be improved.

The area where the layer (A) and the layer (B) are in contact, that is, the area where the layer (B) covers the layer (A), is the area of the layer (A) in the display portion of the organic EL display device in improving light emission reliability. Preferably 5% or more of the total surface area, more preferably 20% or more.

That is, in the organic EL display device of the present invention, in the display portion, the area ratio where the layer (B) covers the surface of the layer (A) is 20 to 100% of 100% of the total surface area of the layer (A). It is desirable to have it. The area ratio that the layer (B) covers the surface of the layer (A) is the ratio that the layer (B) covers the surface of the layer (A) in a square area of 250 μm in length and 250 μm in width selected at random in the display unit. Area, that is, the area of the area where layer (B) is placed on the surface of layer (A) (㎛ ² ) divided by the total surface area of layer (A) (㎛ ² ), multiplied by 100 to the first decimal place It can be calculated by rounding off .

Additionally, the value obtained by subtracting the area of the openings of the layer (A) formed within the same area of 250 μm in height and 250 μm in width in the display section from 62500 μm ² , which is the area of the area of 250 μm in height and 250 μm in width. The total surface area of layer (A) can be considered.

The optical density per 1.0 μm film thickness of the layer (A) is preferably 0.5 or more, and more preferably 0.7 or more in order to improve the effect of suppressing external light reflection and improve luminescence reliability. Moreover, in order to improve light emission reliability, 1.5 or less is preferable, and 1.4 or less is more preferable.

That is, the optical density (OD/μm) per 1.0 μm film thickness of the layer (A) included in the pixel division layer included in the organic EL display device of the present invention is preferably 0.5 to 1.5.

The optical density per 1.0 μm film thickness of the layer (B) is preferably 0.3 or less, and more preferably 0.1 or less in order to improve light emission reliability.

That is, the optical density (OD/μm) per 1.0 μm film thickness of the layer (B) included in the pixel division layer included in the organic EL display device of the present invention is preferably 0.0 to 0.3.

The optical density per 1.0 ㎛ film thickness here refers to measuring the incident light intensity and transmitted light intensity using an optical densitometer (X-Rite 361T manufactured by X-Rite) and dividing the value calculated from the following equation by the film thickness value. It means the value rounded to two decimal places, and the higher the optical density, the higher the light blocking ability.

Optical density = log ₁₀ (I ₀ /I)

I ₀ : Incident light intensity

I: Transmitted light intensity

In the area where the layer (B) is disposed on the surface of the layer (A), the maximum value of the film thickness of the layer (A) is preferably 0.5 μm or more, and more preferably 0.8 μm or more in order to improve light blocking properties. . In order to improve light emission reliability, 3.0 μm or less is preferable, and 2.0 μm or less is more preferable.

In the area where the layer (B) is disposed on the surface of the layer (A), the maximum value of the film thickness of the layer (B) is preferably 0.1 μm or more, and more preferably 0.3 μm or more in order to improve luminescence reliability. desirable. In order to improve light emission reliability, 3.0 μm or less is preferable, and 2.0 μm or less is more preferable.

That is, in the organic EL display device of the present invention, the maximum film thickness of the layer (A) is 0.5 to 3.0 ㎛ in the area where the layer (B) is disposed on the surface of the layer (A), and the layer (B) has a maximum thickness of 0.5 to 3.0 μm. ) It is desirable to have a region where the maximum film thickness is 0.1 to 3.0 μm.

Here, the maximum value of the film thickness of layer (A) and the maximum value of the film thickness of layer (B) are the layers within a randomly selected area of 250 μm in height and 250 μm in width in the display portion of the organic EL display device. The maximum film thickness of layer (A) and the maximum film thickness of layer (B) can be calculated by rounding off the two decimal places of the measured values.

The film thicknesses of layer (A) and layer (B) can be measured by observing the cross section of the pixel division layer using a scanning electron microscope (hereinafter referred to as “SEM”) and taking images thereof. In the case where the two layers are mixed or fused together on the surface where the layers (A) and (B) are in contact to form an intermediate layer, the area corresponding to the center of the intermediate layer in the film depth direction is the interface between the layers (A) and (B). The film thickness can be measured separately by considering . Methods other than SEM include a method using a stylus-type film thickness measuring device.

The cross-sectional taper angle of the end of the pixel dividing layer at the boundary with the opening of the pixel dividing layer is preferably 50° or less, and is 40° in order to improve the film forming properties of the second electrode and suppress non-lighting of the light emitting pixel. The following is more preferable. In order to improve the light-shielding property of the edge of the opening of the pixel dividing layer, 15° or more is preferable, and 20° or more is more preferable. Also, from the same point of view, it is preferable that both layers are arranged so that the opening width of the openings in layer (A) is the same or narrower than that of the openings in layer (B). That is, it is preferable that the end portion of the opening of the pixel dividing layer has light-shielding properties derived from the layer (A).

In order to improve the luminescence reliability of the organic EL display device, it is preferable that the layer (A) in the display portion has an opening with an opening area of 30.0 μm ² or more where the luminescent pixels are arranged. In addition, since the number of light-emitting pixels that can be arranged per unit area can be increased and display quality can be improved, it is preferable to have an opening where the light-emitting pixels are arranged with an opening area of 260.0 ㎛ ² or less.

That is, in the organic EL display device of the present invention, the layer (A) preferably has an opening with an opening area of 30.0 to 260.0 μm ² in the display portion where the light-emitting pixels are arranged.

The shape of each opening is not particularly limited. For example, a circular opening with a diameter of 7 to 18 μm or a square opening with a side of 6 to 16 μm may be used. The smaller the area per light-emitting pixel, the more significant the excellent technical effect of the present invention, such as high light emission reliability, becomes.

As a specific example of the embodiment of the present invention, in the display portion, a layer (A) having hole pattern-shaped openings in which the opening area where the light-emitting pixels are arranged is within the range of 30.0 to 260.0 μm ² is shown in FIG. 8. FIG. 9 shows a layer (A) having square pattern-shaped openings in which the light-emitting pixels are arranged and the opening area is in the range of 30.0 to 260.0 μm ^{2 .}

The layer (A) contains as essential components a cured product of the negative photosensitive composition (a) containing a pigment and/or dye, a compound having two or more ethylenically unsaturated double bond groups in the molecule, and a photopolymerization initiator. The film containing the cured product is sometimes called a cured film. The content of the cured product of the negative photosensitive composition (a) is preferably 99% by weight or more in the layer (A) in order to improve luminescence reliability. A negative photosensitive composition refers to a pattern formed by removing the film of the unexposed area with an alkaline developer by making the alkali solubility of the film of the exposed area relatively low compared to the alkali solubility of the film of the unexposed area by pattern exposure through a negative exposure mask. , refers to a composition with negative photosensitivity.

The layer (B) contains as an essential component a cured product of the positive photosensitive composition (b) containing a resin and a photoacid generator. The film containing the cured product is sometimes called a cured film. The content of the cured product of the positive photosensitive composition (b) is preferably 99% by weight or more in the layer (B) in order to improve luminescence reliability. A positive type photosensitive composition is a positive type photosensitive composition in which a pattern is formed by removing the film of the exposed area with an alkaline developer by making the alkali solubility of the film of the exposed area relatively high compared to the alkali solubility of the film of the unexposed area by pattern exposure through a positive exposure mask. It refers to a composition having type photosensitivity.

The cured product of the negative photosensitive composition (a) herein refers to a product obtained by a method that includes at least the step of heat-treating the negative photosensitive composition (a) at a heating temperature of 200°C or higher for 10 minutes or more. It means water. The cured product of the positive photosensitive composition (b) refers to water obtained by a method that includes at least a step of heat-treating the positive photosensitive composition (b) under room temperature conditions of 200°C or higher for 10 minutes or more.

The layer (A) contains the cured product of the negative photosensitive composition (a) as an essential component, and the layer (B) contains the cured product of the positive photosensitive composition (b) as an essential component, but the technical effect of the present invention is achieved. It is okay to contain other ingredients as long as they do not cause harm. Other components include, for example, moisture adsorbed on the cured product of the negative photosensitive composition (a) or the cured product of the positive photosensitive composition (b). The total amount of other components is preferably 1% by weight or less in each layer (A) or layer (B).

The negative photosensitive composition (a) contains pigment and/or dye. Light-shielding properties can be imparted to the layer (A) by containing pigment and/or dye. As the pigment, a benzodifuranone-based black pigment is preferred because it has excellent light-shielding properties and luminescence reliability. The benzodifuranone-based black pigment is an organic black pigment composed of a compound having in the molecule a polycyclic structure in which two furanone rings are condensed to one benzene ring, for example, bis- described in International Publication No. 2009/010521. Oxodihydroindolylene-benzodifuranone can be mentioned. Among these, in order to improve luminescence reliability, it is preferable that the cured product of the negative photosensitive composition (a) contains a benzodifuranone-based black pigment represented by formula (1) or formula (2). It is more preferable that the cured product of the negative photosensitive composition (a) contains the benzodifuranone-based black pigment represented by formula (3). In formula (3), R ¹ to R ¹⁰ in formula (1) are hydrogen atoms. Commercially available products of the benzodifuranone-based black pigment represented by formula (3) include Irgaphor Black (registered trademark) S0100CF and Experimental Black 582 (all manufactured by BASF). In improving the resolution of the layer (A), the benzodifuranone-based black pigment represented by formula (1) or formula (2) is formed on the pigment surface by a coating layer containing silica, metal oxide, and/or metal hydroxide. It is desirable that at least part of it is covered. In order to improve the resolution of the layer (A), it is more preferable that the cured product of the negative photosensitive composition (a) further contains the compound represented by formula (4) or a salt thereof. By containing the benzodifuranone-based black pigment represented by Formula (1) or Formula (2) in the negative photosensitive composition (a), the cured product of the negative photosensitive composition (a) is coated with Formula (1) or Formula ( The benzodifuranone-based black pigment represented by 2) can be contained.

In formulas (1) and (2), R ¹ to R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, or a carboxyl group.

In improving the luminescence reliability, the cured product of the negative photosensitive composition (a) is C. I. Pigment Red 123, C. I. Pigment Red 149, C. I. Pigment Red 178, C. I. Pigment Red 179, C. I. Pigment Red 190, C. I. It is preferable to contain at least one type of perylene-based organic pigment selected from the group consisting of Pigment Violet 29 and 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole. It is more preferable to contain 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole.

That is, the cured product of the negative photosensitive composition (a) contained in the layer (A) of the organic EL display device of the present invention further contains 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole. It is more preferable to contain it.

The term 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole herein includes the compound represented by formula (5), which is a cis chain, and the compound represented by formula (6), which is a trans chain.

By containing the above-mentioned perylene-based organic pigment in the negative photosensitive composition (a), the above-mentioned perylene-based organic pigment can be contained in the cured product of the negative photosensitive composition (a).

As other pigments, for example, C. I. Pigment Yellow 151, 175, 180, 185, 192, C. I. Pigment Red 254, 255, 264, C. I. Pigment Orange 43, 61, 72, C. I. Pigment Blue 15:3, 15. :4, 15:6, 25, 26, 60, 65, 80, C.I. You may use together organic pigments such as Pigment Violet 19, 29, 32, 37, and inorganic pigments such as carbon black, titanium nitride, and zirconium nitride. .

As dyes, from the viewpoint of solubility in solvents and developability, oil-soluble dyes and acid dyes are preferable, for example, red dyes such as C.I. Solvent Red 46, 72, C.I. Acid Red 52, 87, 289, 388, etc. , yellow dyes such as C.I. Solvent Yellow 93, blue dyes such as C.I. Solvent Blue 35, 45, 97, 104, 122, C.I. Acid Blue 9, 25, 27, 40, 80, 90, 112, 127, 129, 145, etc., Purple dyes such as C.I. Solvent Violet 9, 13, 43, C.I. Acid Violet 29, 31, 33, 36, 39, 48, 63, 109, and black dyes such as C.I. Solvent Black 27, 29, 34, and C.I. Acid Black 52. I can hear it. If necessary, the solubility in the solvent may be improved by salting the acidic dye with a basic dye or a cationic component.

The negative photosensitive composition (a) may contain pigments and dyes, and the total of their contents is 10 to 50% by weight of the solid content of the negative photosensitive composition (a), in order to achieve both light-shielding properties and resolution of the layer (A). Weight percent is preferred. The above-mentioned organic pigments and dyes are transparent to near-infrared rays, and enable high-precision automatic alignment, that is, near-infrared alignment, of the substrate on which the prebake film is formed and the exposure mask using a near-infrared camera, thereby improving the yield during panel production. You can.

The negative photosensitive composition (a) contains a compound having two or more ethylenically unsaturated double bond groups in the molecule. In the case of compounds having two or more ethylenically unsaturated double bond groups in the molecule, the photocuring reaction proceeds in chain by radical active species that generate a photopolymerization initiator, which will be described later, and the alkali solubility of the film in the exposed area is changed to the alkali solubility of the film in the unexposed area. In comparison, this has the effect of making it relatively low, and pattern formation by negative photolithography becomes possible. Specific examples include "KAYARAD" (registered trademark) DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, ZAR-1494H, ZAR-2001H, ZFR-1491H, ZCR- 1569H, ZCR-1797H, ZCR-1798H, ZCR-1761H, CCR-1171H, CCR-1291H, CCR-1307H, CCR-1309H (all manufactured by Nippon Kayaku Co., Ltd.), "Light Acrylate" (registered trademark) BP-4EAL, BP-4PA (all manufactured by Kyoeisha Kagaku Co., Ltd.), "OGSOL" (registered trademark) EA-0200, EA-0250P, EA-0300, CR -1030 (above, all manufactured by Osaka Gas Chemical Co., Ltd.), alkali-soluble epoxy acrylate resin containing an unsaturated double bond group having a structural unit represented by formula (7), an unsaturated double bond group having a structural unit represented by formula (8) and an alkali-soluble polyimide precursor containing a linking group. It does not matter whether these are used alone or in combination. In addition, a compound having two or more ethylenically unsaturated double bond groups in the molecule, and a compound corresponding to an alkali-soluble resin described later, is defined as a component belonging to a compound having two or more ethylenically unsaturated double bond groups in the molecule.

The content of the compound having two or more ethylenically unsaturated double bond groups in the molecule is preferably 10 to 60% by weight based on 100% by weight of solid content of the negative photosensitive composition in order to achieve both film adhesion and resolution in the development process. do.

In formula (7), R ³⁴ and R ³⁵ each independently represent a hydrogen atom or a methyl group. * indicates the bonding site with a carbon atom.

In formula (8), R ³⁶ represents a tetravalent organic group containing an aromatic ring or cyclic aliphatic ring. R ³⁷ represents a trivalent organic group containing an aromatic ring or cyclic aliphatic ring. R ³⁸ represents an alkylene group having 1 to 5 carbon atoms. R ³⁹ represents a hydrogen atom or a methyl group. * indicates binding site.

The negative photosensitive composition (a) contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that generates radical active species by exposure to near-ultraviolet rays. Examples of the photopolymerization initiator include an oxime ester-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator. Among them, an oxime ester-based photopolymerization initiator is preferable in improving the adhesion of the film in the development process, for example, "Adeca Cools" (registered trademark) NCI-831E, N-1919T (all ADEKA (Co., Ltd.), "Irgacure" (registered trademark) OXE01, OXE02, OXE03, OXE04, and compounds represented by formula (9). The content of the photopolymerization initiator is preferably 1 to 10% by weight based on 100% by weight of solid content of the negative photosensitive composition in order to achieve both film adhesion and resolution in the development process.

In order to improve the resolution of the layer (A), the negative photosensitive composition (a) preferably further contains an alkali-soluble resin. The alkali-soluble resin referred to here is a solution obtained by dissolving the resin in γ-butyrolactone, applied to the surface of a silicon wafer, prebaked for 4 minutes on a hot plate at a room temperature of 120°C, and prebaked to a film thickness of 10 ± 0.5 ㎛. After forming the film, the prebaked film was immersed in an alkaline developer, 2.38% by weight tetramethylammonium hydroxide aqueous solution at 23 ± 1°C, for 1 minute, and then rinsed with pure water at 23 ± 1°C for 10 seconds, and then the amount of film loss was obtained. Resin refers to a resin with a dissolution rate in the membrane depth direction of 50 nm/min or more. Resin refers to a compound that has a weight average molecular weight (Mw) of 1000 or more and has a polymer chain composed of repeating structural units.

Examples of alkali-soluble resin include alkali-soluble phenol resin, alkali-soluble (meth)acrylic resin, alkali-soluble polyhydroxystyrene, alkali-soluble polyimide, alkali-soluble polyimide precursor, alkali-soluble polybenzoxazole, and alkali-soluble polybenzo. Examples include oxazole precursors, alkali-soluble polysiloxanes, and alkali-soluble polyamines. It does not matter whether these are used alone or in combination. The alkali-soluble polyimide precursor referred to herein means a resin that is converted into polyimide by forming an imide bond through heat treatment, and specific examples include polyamic acid and polyamic acid ester.

Among them, in order to lower the cross-sectional taper angle at the end of the layer (A) and improve resolution, it is preferable to contain an alkali-soluble phenolic resin, an alkali-soluble (meth)acrylic resin, and/or an alkali-soluble polyimide. do. Additionally, it is preferable to contain an alkali-soluble polyamine as a pigment dispersant. (meth)acrylic resin means methacrylic resin or acrylic resin. Examples of alkali-soluble phenol resins include novolak-type phenol resins and resol-type phenol resins, as well as novolak-type phenol resins having a polymer chain made of polyhydroxystyrene described in Japanese Patent Application Laid-Open No. 2010-106278, and known It can be synthesized by the method. Aldehyde compounds such as formaldehyde and benzaldehyde are added to compounds having a phenol skeleton such as phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, and 3,5-xylenol using an acidic catalyst or It is obtained by reacting in the presence of a basic catalyst. Examples of commercially available products include TRR5030G, TRR5010G, TR4020G, TR4080G, TR4000B, TRM30B20G, and EP23F10G (all manufactured by Asahi Yukizai Co., Ltd.).

As the alkali-soluble polyamine, a resin having two or more tertiary amino groups in the molecule described in Patent Document 1 is preferably used. Examples of the alkali-soluble polyimide include resins having a structural unit represented by formula (10) described later.

The negative photosensitive composition (a) may further contain a solvent. By containing a solvent, the viscosity, thixotropy, etc. of the negative photosensitive composition can be adjusted, and the film thickness uniformity of the coating film can be improved. Examples of solvents include propylene glycol monomethyl ether (hereinafter referred to as PGME), propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”). ), 3-methoxybutylacetate (hereinafter referred to as “MBA”), methyl lactate, ethyl lactate, γ-butyrolactone, valerolactone, and ε-caprolactone. From the viewpoint of storage stability, the moisture content in 100 parts by weight of the negative photosensitive composition (a) is preferably 0.01 to 0.5 parts by weight. In order to obtain higher film thickness uniformity, a leveling agent consisting of a nonionic surfactant may be contained.

In improving the luminescence reliability, the cured product of the negative photosensitive composition (a) contained in the layer (A) has a primary particle diameter of 5 to 30 nm and an aspect ratio (major axis/minor axis) of 1.0 to 1.5. It is preferred that it contains phosphorus silica particles. The silica particles referred to herein are particles with a pure content of SiO ₂ of 90% by weight or more based on the weight excluding water, particles made of silicon dioxide (anhydrous silicic acid), particles made of silicon dioxide hydrate (hydrous silicic acid, white carbon), or quartz glass. It means particles made up of Also encompassed are particles consisting of ortho-silicic acid, meta-silicic acid and/or meta-disilicic acid. The structure of the particles is not particularly limited, and may have internal voids. The aspect ratio referred to here refers to the value obtained by dividing the major axis of a silica particle by its minor axis, rounded off to two decimal places. Additionally, when the aspect ratio is 1.0, it can be regarded as a spherical silica particle. By containing silica particles having a primary particle diameter of 5 to 30 nm and an aspect ratio (major axis/minor axis) of 1.0 to 1.5, or a dispersion liquid containing the same, in the negative photosensitive composition (a), the negative photosensitive composition (a) ) The silica particles can be contained in the cured product.

Commercially available dispersions containing silica particles with a primary particle diameter of 5 to 30 nm and an aspect ratio (major axis/minor axis) of 1.0 to 1.5 include MEK-ST-40 and MEK-ST-L (all Nissan Car products). Product made by Kaku Kogyo Co., Ltd.) can be mentioned. The primary particle diameter and aspect ratio were measured by using a transmission electron microscope (TEM) on a cross-section of a thinly cut pixel division layer as an observation sample and polished by ion milling to increase smoothness. The outermost layer of the pixel division layer was measured. Imaging observed at a location within a range of 0.2 to 0.8 μm in the film depth direction from the film depth direction under the condition of a magnification of 50,000 times can be measured using an image analysis type particle size distribution measuring device “Mac-View” (manufactured by MOUNTECH). Additionally, silica particles can be identified by determining the elements constituting the particles using energy dispersive X-ray spectroscopy (TEM-EDX).

The negative photosensitive composition (a) may further contain a heat crosslinking agent. There are cases where higher luminescence reliability can be obtained by containing an appropriate amount of thermal crosslinking agent within a range that does not impair resolution. As a thermal crosslinking agent, compounds having two or more epoxy groups are preferable, and specific examples include TEPIC-L, TEPIC-S, TEPIC-PAS (all manufactured by Nissan Chemical Industries, Ltd.), NC-3000, XD-1000, An example is the XD-1000H (all from Nippon Kayaku Co., Ltd.).

The positive photosensitive composition (b) contains a resin. The resin is not particularly limited, but examples include the alkali-soluble resin described above.

In order to obtain high luminescence reliability, it is preferable that the cured product of the positive photosensitive composition (b) contained in the layer (B) contains a resin having an imide bond and/or a benzoxazole skeleton. By containing a resin or a precursor thereof having an imide bond and/or benzoxazole skeleton in the positive photosensitive composition (b), the cured product of the positive photosensitive composition (b) contains an imide bond and/or benzoxazole. A resin having a skeleton may be contained. In view of the above, among the alkali-soluble resins described above, the positive photosensitive composition (b) is alkali-soluble polyimide, alkali-soluble polyimide precursor, alkali-soluble polybenzoxazole, alkali-soluble polybenzoxazole precursor and/or copolymers thereof. It is preferable to contain. It is more preferable to contain a resin having a structural unit represented by formula (10) and/or a structural unit represented by formula (11).

In formula (10), R ¹¹ represents a 4- to 10-valent organic group. R ¹² represents a 2-8 valent organic group. R ¹³ and R ¹⁴ each independently represent a phenolic hydroxyl group or a carboxyl group, and each may be a single contribution, or different groups may be mixed. p and q are integers and each independently represents 0 to 6. However, p+q>0 is satisfied. * indicates binding site.

In formula (11), R ¹⁵ and R ¹⁶ represent a divalent to octavalent organic group. R ¹⁷ and R ¹⁸ each independently represent a hydroxyl group, a carboxyl group, or COOA, and each may be a single contribution, or different groups may be mixed. A represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. r and s are integers and each independently represents 0 to 6. However, r+s>2 is satisfied. * indicates binding site.

In formula (11), examples of the monovalent hydrocarbon group A having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, phenyl group, or benzyl group.

The weight average molecular weight (Mw) of the resin having the structural unit represented by formula (10) and/or the structural unit represented by formula (11) is preferably 10,000 or more and 50,000 or less in order to improve resolution.

In formula (10), R ¹¹ -(R ¹³ )p represents the residue of acid dianhydride. R ¹¹ is preferably an organic group containing 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group. Examples of acid dianhydride residues include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyltetracarboxyl. Acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3 '-Benzophenonetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1 -bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2) ,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluoric acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric acid Dianhydride, the residue of aromatic tetracarboxylic dianhydride such as the residue of acid dianhydride of the structure represented by formula (12), butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracar and residues of aliphatic tetracarboxylic dianhydride, such as the residue of boxylic acid dianhydride.

In formula (12), R ¹⁹ represents a single bond, an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ²⁰ and R ²¹ each independently represent a hydrogen atom or a hydroxyl group.

In formula (11), R ¹⁵ -(R ¹⁷ )r represents an acid residue. R ¹⁵ is preferably an organic group containing an aromatic ring or a cyclic aliphatic group and having 5 to 40 carbon atoms.

Examples of acid residues include dicarboxylic acid residues, tricarboxylic acid residues, and tetracarboxylic acid residues. As dicarboxylic acids, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. I can hear it. Examples of tricarboxylic acids include residues of trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. As residues of tetracarboxylic acid, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2' ,3,3'-Biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2 -Bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane , 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl) ) Ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9 , aromatic tetracarboxylic acid residues such as the residues of 10-perylenetetracarboxylic acid, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid residues. A residue of an acid may be mentioned.

R ¹² -(R ¹⁴ )q in formula (10) and R ¹⁶ -(R ¹⁸ )s in formula (11) represent diamine residues. R ¹² and R ¹⁶ are preferably organic groups containing 5 to 40 carbon atoms containing an aromatic ring or cyclic aliphatic group.

Examples of diamine residues include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl. Methane, 1,4-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy) Biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2 ,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobi In addition to phenyl, 9-bis (4-aminophenyl) fluorene residues, or residues of compounds in which at least part of the hydrogen atoms of their aromatic rings are replaced with alkyl groups or halogen atoms, compounds represented by formula (13), formula (14) Examples include residues of the compound represented by, the compound represented by formula (15), and the compound represented by formula (16).

In formula (13), R ²² represents a single bond, an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ²³ and R ²⁴ each independently represent a hydrogen atom or a hydroxyl group.

In formula (14), R ²⁵ represents a single bond, an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ²⁶ and R ²⁷ each independently represent a hydrogen atom or a hydroxyl group.

In formula (15), R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ each independently represent a hydrogen atom or a hydroxyl group.

In formula (16), R ³² and R ³³ each independently represent a hydrogen atom or a hydroxyl group.

Additionally, by sealing the ends of these resins with a monoamine, the weight average molecular weight (Mw) can be easily adjusted during synthesis, and the storage stability as an alkali-soluble resin can be improved.

As monoamines, for example, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxylic -7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-aminophenol, 3-amino Phenol and 4-aminophenol can be mentioned.

In formula (11), the group represented by COOA is obtained by converting the carboxyl group with an esterifying agent. Examples of the esterifying agent include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl acetal.

Resins having the structural unit represented by formula (10) and/or the structural unit represented by formula (11) can be obtained by known methods, for example, Japanese Patent No. 4341293, International Publication No. 2014/097992, It can be synthesized by the method disclosed in International Publication No. 2019/181782.

In order to improve luminescence reliability, the resin content is preferably 50 to 90% by weight based on 100% by weight of solid content of the positive photosensitive composition (b).

The positive photosensitive composition (b) contains a photoacid generator. The photoacid generator is not particularly limited as long as it is a compound that decomposes upon irradiation of near-ultraviolet light and generates acid. The generated acid has the effect of increasing the alkali solubility of the film in the exposed area relatively compared to the alkali solubility of the film in the unexposed area, making pattern formation by positive photolithography possible. Examples of the acids generated include indenecarboxylic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid.

Examples of photoacid generators include quinonediazide compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among them, quinonediazide compounds that generate carboxylic acid and/or sulfonic acid as acids by irradiation of near-ultraviolet light are preferable in improving luminescence reliability. As the quinonediazide compound, a compound having a phenolic hydroxyl group and 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (hereinafter referred to as “4-naphthoquinone diazide sulfonylic acid chloride”) There is a 4-naphthoquinone diazide sulfonyl ester compound, which is a compound obtained by the esterification reaction of), a compound having a phenolic hydroxyl group, and 1,2-naphthoquinone-2-diazide-5-sulfonyl ester compound. 5-Naphthoquinone diazidesulfonyl ester compound, a compound obtained by esterification of phenyl chloride (hereinafter sometimes referred to as “5-naphthoquinone diazidesulfonylic acid chloride”), Japanese Patent Publication 2019- Examples include naphthoquinone diazide sulfonic acid derivatives described in No. 174793. Compounds having a phenolic hydroxyl group include, for example, TrisP-HAP, TrisP-PA, TekP-4HBPA, TrisP-SA, TrisOCR-PA, BisP-AP, BisP-NO, BisP-PR, BisP-B, BisP-DE. , BisP-DP, BisP-DP, BisRS-2P, BisRS-3P, and BisP-DEK (all manufactured by Honshu Kagaku Kogyo Co., Ltd.). Commercially available products of 5-naphthoquinone diazide sulfonyl ester compounds include, for example, 4NT-250 and 4NT-300 (manufactured by Toyo Kose Kogyo Co., Ltd.). The content of the photoacid generator is preferably 1 to 40% by weight based on 100% by weight of solid content of the positive photosensitive composition (b) in order to improve exposure sensitivity.

The positive photosensitive composition (b) may further contain a heat crosslinking agent. By containing a thermal crosslinking agent, better luminescence reliability is obtained. As a thermal crosslinking agent, a compound having two or more alkoxyalkyl groups in the molecule is preferable. Examples of the alkoxyalkyl group include methoxymethyl group, ethoxymethyl group, propoxymethyl group, and butoxymethyl group. Preferred examples of compounds having two or more alkoxymethyl groups in the molecule include compounds represented by formula (17), compounds represented by formula (18), and compounds represented by formula (19).

The positive photosensitive composition (b) may further contain the above-mentioned solvent. By containing a solvent, the viscosity, thixotropy, etc. of the positive photosensitive composition can be adjusted, and the film thickness uniformity of the coating film can be improved.

The organic EL display device of the present invention may contain a pigment and/or dye in the layer (B) as in the layer (A), as long as the effect of the present invention is not impaired. However, in order to obtain high luminescence reliability, the total content of the pigment and dye is preferably 5 parts by weight or less, and more preferably 0 parts by weight, based on 100 parts by weight of the layer (B).

That is, the organic EL display device of the present invention is an organic EL display device comprising a substrate, a planarization layer, a first electrode, a pixel split layer, a light-emitting pixel, and a second electrode in this order, and the pixel split layer is a layer (A). ) and a layer (B), wherein the layer (A) is a layer disposed on the surface of the first electrode by partially exposing the surface of the first electrode, and the layer (B) is the layer (A) A negative photosensitive composition (a) is a layer disposed on at least a portion of the surface of ), wherein the layer (B) contains a cured product of a positive photosensitive composition (b) containing a resin and a photoacid generator, and the content of pigment and/or dye in the layer (B) is It is preferable that the total amount be 5 parts by weight or less out of 100 parts by weight of the layer (B) in an organic EL display device.

A method of forming the layer (A) using the negative photosensitive composition (a) includes an application process of applying the negative photosensitive composition (a) to obtain a coating film, and an active chemical treatment including near-ultraviolet rays through a negative exposure mask. An exposure process to obtain an exposed film having an exposed portion and an unexposed unexposed portion in a surface by exposing lines in a pattern, a development process to obtain a developed film by developing using an alkaline developer, and obtaining a cured film by thermosetting by heating. A method including a cure process is preferred.

A method of forming the layer (B) using the positive photosensitive composition (b) includes an application step of applying the positive photosensitive composition (b) to obtain a coating film, and an active chemical treatment including near-ultraviolet rays through a positive exposure mask. A method comprising an exposure process to obtain an exposed film having exposed and unexposed parts in a plane by exposing lines in a pattern, a developing process to obtain a developed film by developing using an alkaline developer, and a cure process to obtain a cured film by thermosetting by heating. This is desirable.

As a coating device used in the coating process, a spin coater or a slit coater can be preferably used because of its excellent thin film coating properties. After application, pin gap prebake or contact prebake may be performed. The prebake temperature is preferably 50 to 150°C, and the prebake time is preferably 30 seconds to 5 minutes.

Examples of exposure devices used in the exposure process include steppers, mirror projection mask aligners (MPA), and parallel light mask aligners (PLA). Active actinic rays including near-ultraviolet rays irradiated during exposure include j-rays (wavelength 313 nm), i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), or g-rays (wavelength 436 nm) of mercury lamps, i A line or a mixed line including the g-line, h-line, and i-line is preferable. Examples of the negative exposure mask and the positive exposure mask include a mask in which a light-shielding portion made of a metal such as chromium is formed in a pattern on the surface of one side of a substrate having a near-ultraviolet transmission portion such as glass, quartz, or film. By pattern-exposing only the openings through active actinic rays, an exposed film having an exposed portion and an unexposed portion in a plane is obtained. In addition, by performing pattern exposure using a halftone exposure mask having a fully transmissive portion and a semi-transmissive portion with different transmittances of active actinic rays in the plane, a convex-shaped thick film portion is collectively formed, and a spacer function is provided to at least a portion of the pixel division layer. You may grant it.

Examples of the development method in the development process include shower, dipping, and paddle methods, and include a method of immersing the exposure film for 10 seconds to 3 minutes. The paddle method is preferable in increasing the in-plane uniformity of the opening width of the opening. As an alkaline developer, a 1.0 to 2.5% by weight aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) is preferable, and a commercially available product includes a 2.38% by weight TMAH aqueous solution (manufactured by Tama Chemical Co., Ltd.). After the development process, a cleaning treatment using a shower of deionized water and/or a moisture removal treatment using air injection may be added.

In the cure process, the developing film is thermoset by heating and moisture, developer, etc. are volatilized. Examples of heating devices include hot air ovens and IR ovens. The heating temperature is preferably 200 to 350°C under atmospheric pressure, and more preferably 220 to 280°C.

As a method of preparing a negative photosensitive composition (a) containing a pigment, a pigment dispersion is prepared by wet dispersion treatment, and then a compound having two or more ethylenically unsaturated double bond groups in the molecule, a photopolymerization initiator, and, if necessary, a solvent. After mixing other components, such as adding them to the pigment dispersion, they are mixed, stirred, and, if necessary, filtered using a filtration filter. For wet dispersion treatment, it is preferable to use a wet media disperser such as a bead mill because it has excellent dispersion speed and strong disintegration power, making it economically advantageous. The cumulative 50% particle diameter of the pigment in the pigment dispersion and in the negative photosensitive composition (a) prepared using it is preferably 20 nm or more, and more preferably 40 nm or more, respectively, in order to improve luminescence reliability. From the same point of view, 100 nm or less is preferable, and 80 nm or less is more preferable. The cumulative 50% particle diameter is the particle diameter corresponding to the cumulative 50% of the cumulative distribution curve of the particle diameter based on the light scattering intensity for the light source (semiconductor excited solid-state laser with a wavelength of 532 nm/10 mW). The cumulative 50% particle diameter can be calculated using the particle size distribution measuring device "SZ-100" of the dynamic light scattering method, using the fine particle diameter side as the starting point (0%). In addition, the maximum particle diameter is preferably 400 nm or less, and more preferably 300 nm or less in order to improve light emission reliability.

On the other hand, as a method of preparing the negative photosensitive composition (a) containing a dye, the wet dispersion treatment step described above is not necessary, and other than performing a step of adding and dissolving the dye in a resin or a resin solution, the pigment is It can be prepared in the same way as when containing it.

Methods for preparing the positive photosensitive composition (b) include mixing and stirring the resin, the photoacid generator, and, if necessary, other components such as a solvent, and performing filtration using a filtration filter as needed.

Example

The present invention will be described in detail below by giving examples and comparative examples, but the form of the present invention is not limited to these.

First, the evaluation method in each Example and Comparative Example will be explained.

<Measurement of the optimal exposure amount (A) of the negative photosensitive composition when forming layer (A)>

A first electrode formation substrate provided with a first electrode consisting of a lamination pattern of a silver alloy film/low crystallinity ITO was produced in the same manner as the method described in Example 1 described later.

The negative photosensitive composition was applied to the ITO surface of the first electrode forming substrate using a spin coater, adjusting the rotation speed so that the finally obtained cured film had the desired film thickness, to obtain a coating film. Additionally, using a hot plate, the coating film was prebaked at 110°C under atmospheric pressure for 120 seconds to obtain a prebaked film. The negative square pattern exposure mask is aligned using a near-infrared camera, and a double-sided alignment single-side exposure device is used to create a negative square pattern exposure mask (1,000 square light-shielding portions with a vertical width of 7.0 μm and a horizontal width of 7.0 μm are arranged). ), the exposure amount is changed step by step every 5 mJ within the range of 10 to 100 mJ (mJ/cm2: i line conversion value), and the g, h, and i mixed lines of the ultra-high pressure mercury lamp are pattern exposed, and the exposed area and mino An exposed film having a light portion in the plane was obtained. In addition, pattern exposure was performed by bringing a negative square pattern exposure mask into contact with the surface of the prebake film. Next, using a small developing device for photolithography (AD-2000; manufactured by Takizawa Sankyo Co., Ltd.), development was performed using a paddle method with a 2.38% by weight TMAH aqueous solution, which is an alkaline developer. The paddle method referred to here refers to a method in which a developer is shower applied to the surface of the exposure film for 10 seconds, the alkaline developer is placed on the surface of the prebake film, and then the entire substrate is left standing until a predetermined development time is reached and developed. In addition, the development time was set as the time for the film of the unexposed area to be dissolved and removed in the film depth direction multiplied by 1.5. Additionally, after rinsing in a shower using deionized water for 30 seconds, the substrate was dried by idling at 200 rpm for 30 seconds to obtain a developing film forming substrate having a pattern-shaped developing film. Next, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.), the developing film is heated at 250°C for 1 hour in an air atmosphere to cure the cured product containing the negative photosensitive composition. got the curtain The cured film was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), and the average value of the aperture width of 10 openings in the area of each exposure dose was determined to be the bias with respect to the width of the light-shielding portion of the exposure mask. The minimum exposure amount (mJ/cm2: i-line conversion value) when the opening is within the range of ±0.1㎛ (i.e., 7.0±0.1㎛) is determined as the optimal exposure amount ( It was done as A).

<Measurement of the optimal exposure amount (B) of the positive photosensitive composition when forming layer (B)>

The positive photosensitive composition is applied to the surface of the cured film containing the cured product of the negative photosensitive composition obtained at the above-described optimal exposure dose using a spin coater, adjusting the rotation speed so that the final cured film has the desired film thickness. , a coating film was obtained. Additionally, using a hot plate, the coating film was prebaked at 110°C under atmospheric pressure for 120 seconds to obtain a prebaked film. The position of the positive square pattern exposure mask is aligned with a near-infrared camera, and a positive square pattern exposure mask (1,000 square transparent parts with a vertical width of 7.0 ㎛ and a horizontal width of 7.0 ㎛ arranged) is used using a double-sided alignment single-side exposure device. Through this, the exposure amount is changed step by step every 5 mJ within the range of 50 to 150 mJ (mJ/cm2: i line conversion value), and the g, h, and i mixed lines of the ultra-high pressure mercury lamp are exposed in a pattern, exposing the exposed and unexposed areas. An exposed film having in-plane was obtained. In addition, pattern exposure was performed by bringing a positive square pattern exposure mask into contact with the surface of the prebake film.

Next, using a small developing device for photolithography, development was performed for 80 seconds using a paddle method with a 2.38% by weight TMAH aqueous solution. The film thickness of the prebaked film and the developing film of the positive photosensitive composition were each obtained from the difference between the film thickness of the laminated film and the film thickness of the cured film containing the cured product of the negative photosensitive composition. Additionally, after rinsing in a shower using deionized water for 30 seconds, the substrate was dried by idling at 200 rpm for 30 seconds to obtain a developing film forming substrate having a pattern-shaped developing film. Next, using a high-temperature inert gas oven, the developing film was heated at 250°C in an air atmosphere for 1 hour to obtain a cured film containing the cured product of the positive photosensitive composition. The cured film is observed using an FPD inspection microscope, and the average value of the opening widths of 10 openings in the area of each exposure dose has a bias of ±0.1 ㎛ (i.e., 7.0 ± 0.1 ㎛) with respect to the width of the transmission portion of the exposure mask. The minimum exposure amount (mJ/cm2: i-line conversion value) when the opening is within the range was set as the optimal exposure amount (B) of the positive photosensitive composition used to form the layer (B).

<Measurement of the optimal exposure dose (A) of the positive photosensitive composition when forming layer (A) and the optimal exposure dose (B) of the negative photosensitive composition when forming layer (B)>

When forming a cured film containing a cured product of a negative photosensitive composition on the surface of a cured film containing a cured product of a positive photosensitive composition, the order of pattern formation described above is reversed and used to form the layer (A). The optimal exposure amount (A) of the positive photosensitive composition used to form the layer (B) and the optimal exposure amount (B) of the negative photosensitive composition used to form the layer (B) were respectively measured in this order.

<Measurement of the optimal exposure amount (B) of the negative photosensitive composition when forming the layer (B)>

When forming a cured film containing a cured product of a negative photosensitive composition on the surface of a cured film containing a cured product of a negative photosensitive composition, the optimal exposure amount of the negative photosensitive composition used for forming the above-described layer (A) is ( In addition to A), the optimal exposure amount (B) of the negative photosensitive composition used for forming the layer (B) was measured in the same manner.

In measuring the optimal exposure amount using a negative or positive square pattern exposure mask in the various configurations above, if the shape of the opening of the cured film is not square, the short side of the opening is regarded as the opening width, and each The average value of the aperture widths of 10 openings in the exposure dose area was determined, and the optimal exposure dose (A) and optimal exposure dose (B) were measured. However, the cured film in which an opening with an aspect ratio of 1.1 or more is included in the surface was excluded from the measurement object. The aspect ratio referred to here refers to the value obtained by dividing the length of the long side of the opening (㎛) by the length of the short side (㎛), rounded off to two decimal places. In addition, the film thickness of the cured film was determined by observing the cross sections of the films corresponding to the layer (A) and layer (B) with an SEM and measuring them based on the imaging.

In addition, the measurement of the optimal exposure amount using a negative or positive hole pattern exposure mask is performed in the same manner as the measurement of the optimal exposure amount using the negative or positive square pattern exposure mask described above, and the shape of the opening of the cured film is determined. If it is formed in a circular shape, its diameter is regarded as the aperture width, and if it is formed in an oval shape, its minor axis is regarded as the aperture width. The average value of the aperture widths of 10 openings in the area of each exposure amount is calculated, and the optimal exposure amount (A) and The optimal exposure dose (B) was measured. However, the cured film in which an opening with an aspect ratio of 1.1 or more is included in the surface was excluded from the measurement object. The aspect ratio referred to here refers to the value obtained by dividing the length of the major axis of the opening (㎛) by the length of the minor axis (㎛), rounded off to two decimal places.

(1) Evaluation of the optical density (OD/㎛) of the cured film

For the optical density evaluation substrates obtained in Examples 1 to 11, on which a cured film with a film thickness of 1.5 μm was formed, an optical density meter (X-Rite manufactured by X-Rite; The total optical density (Total OD value) was measured and the average value was calculated. The value obtained by dividing the average value by 1.5 and rounding off the two decimal places was taken as the OD value per 1.0 μm of the film thickness of the cured film (OD/μm). Evaluation was performed based on the standard that the higher the OD/μm, the better the light-shielding properties of the cured film. As a result of separately measuring the OD value of Tempax on which no cured film was formed, it was 0.00, so the OD value of the substrate for optical density evaluation was regarded as the OD value of the cured film. The film thickness of the cured film was obtained by rounding off the two decimal places of the average value measured at three locations within the surface using a stylus-type film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom). In addition, in cases where the above-mentioned optimal exposure amount could not be measured due to insufficient resolution, evaluation was not possible.

(2) Evaluation of resolution of display part of organic EL display device

The organic EL display devices obtained in Examples 1 to 15, Comparative Examples 1 to 2, and Comparative Examples 4 to 14 were left standing at room temperature with the light emitting surface facing up and emitting light by direct current driving at 10 mA/cm2, and the light emitting pixel portion was left to stand at room temperature. The light-emitting pixel portion located in the center was enlarged and displayed on the monitor and measured. When the average value of the minor diameter (diameter in the case of a perfect circle, short axis in the case of an elliptical shape) of 20 light-emitting pixel portions was less than 20.0 μm, the resolution of the display portion of the organic EL display device was excellent and was passed. On the other hand, in the case of 20.0 μm or more, the resolution of the display portion of the organic EL display device was insufficient and it was disqualified. In addition, when one or more non-lighting pixels were visible, the test was disqualified regardless of resolution.

(3) Evaluation of luminescence reliability of organic EL display devices (high temperature continuous operation test)

The organic EL display devices obtained in Examples 1 to 12, Comparative Examples 1 to 2, and Comparative Examples 4 to 11 were placed with the emitting surface facing upward on a hot plate maintained at a temperature of 85°C by direct current driving at 10 mA/cm2. Politics was carried out with enthusiasm. The 20 light-emitting pixel parts located in the central part of the light-emitting pixel part are observed by enlarging them on the monitor, and the area ratio of the light-emitting part to the area of the light-emitting pixel part (pixel emission area ratio) is measured 1 hour after the start of operation. and measured after 200 hours.

It is said that pixel shrinkage (non-light-emitting area) is less likely to occur, and based on the pixel light-emitting area rate after 1 hour, the higher the pixel light-emitting area rate after 200 hours can be maintained, the better the light emission reliability is. An example of the layer (A), the light-emitting portion, and the non-light-emitting portion when observing the light-emitting pixel portion is shown in Figure 10.

Evaluation was made based on the following criteria, with AA and A to C being passed and D to F being rejected. In addition, in the case where an opening having the desired opening width could not be formed in the measurement of the above-described optimal exposure amount, a fair evaluation was difficult, so the evaluation was set as F.

AA: The pixel emission area ratio is 95% or more.

A: The pixel emission area ratio is 90% or more and less than 95%.

B: The pixel emission area ratio is 85% or more and less than 90%.

C: The pixel emission area ratio is 80% or more and less than 85%.

D: The pixel emission area ratio is 75% or more and less than 80%.

E: The pixel emission area ratio is less than 75%.

F: It is difficult to evaluate the pixel emission area ratio due to lack of resolution.

(4) Evaluation of luminescence reliability of organic EL display devices (light fastness test)

The organic EL display devices obtained in Examples 13 to 15 and Comparative Examples 12 to 14 were made to emit light at room temperature by direct current driving at 10 mA/cm2 with the light emitting surface facing upward. The display portion of the organic EL display device was kept in a state of emitting light, and light with an illuminance of 3.0 W/cm2 at a wavelength of 420 nm, using a xenon lamp as a light source, was continuously irradiated as pseudo-sunlight containing near-ultraviolet rays. The 20 light-emitting pixel parts located in the central part of the light-emitting pixel part are observed by enlarging them on the monitor, and the area ratio of the light-emitting part to the area of the light-emitting pixel part (pixel emission area ratio) is measured 1 hour after the start of operation. and measured after 200 hours. It is said that pixel shrinkage (non-light-emitting area) is less likely to occur, and based on the pixel light-emitting area rate after 1 hour, the higher the pixel light-emitting area rate after 200 hours can be maintained, the better the light emission reliability is. Evaluation was made based on the following criteria, with AA and A to C being passed and D to F being rejected. In addition, in the case where an opening having the desired opening width could not be formed in the measurement of the above-described optimal exposure amount, a fair evaluation was difficult, so the evaluation was set as F.

AA: The pixel emission area ratio is 95% or more.

A: The pixel emission area ratio is 90% or more and less than 95%.

B: The pixel emission area ratio is 85% or more and less than 90%.

C: The pixel emission area ratio is 80% or more and less than 85%.

D: The pixel emission area ratio is 75% or more and less than 80%.

E: The pixel emission area ratio is less than 75%.

F: It is difficult to evaluate the pixel emission area ratio due to lack of resolution.

Below, information on various raw materials used in examples and comparative examples is shown. “Benzodifuranone-based black pigment A”: A black pigment consisting of 100 parts by weight of the benzodifuranone-based black pigment represented by formula (3) as the core and 10 parts by weight of silica as the coating material. It corresponds to the benzodifuranone-based black pigment 2 having a coating layer made of silica on the surface described in Synthesis Example 3 of Patent Document 1 (International Publication No. 2021/111860). Specific surface area 40㎡/g by BET method.

「C. I. Pigment Red 179”: As a commercial product, “PALIOGEN” (registered trademark) RED L3875 (manufactured by BASF) was used.

「C. I. Pigment Violet 29”: As a commercial product, “PALIOGEN” (registered trademark) REDVIOLET K5411 (manufactured by BASF) was used.

“Pigment dispersant 1”: Compound represented by formula (20). Alkali soluble polyamine (100% by weight solids). It corresponds to dispersant 5 described in Patent Document 1 (International Publication No. 2021/111860).

“TR4020G”: A novolak-type phenolic resin that is an alkali-soluble phenolic resin without an ethylenically unsaturated double bond group. Solid content: 100% by weight (made by Asahi Yukizai).

“ZCR-1569H”: PGMEA solution of alkali-soluble epoxy acrylate having a biphenyl skeleton. Solid content: 70% by weight (manufactured by Nippon Kayaku Co., Ltd.). A compound having two or more ethylenically unsaturated double bond groups in the molecule.

“DPCA-20”: “KAYARAD” (registered trademark) DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.). A compound that has six ethylenically unsaturated double bond groups in the molecule. Solid content 100% by weight.

“DPCA-60”: “KAYARAD” (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.). A compound that has six ethylenically unsaturated double bond groups in the molecule. Solid content 100% by weight.

“EA-0250P”: “OGSOL” (registered trademark) EA-0250P (manufactured by Osaka Gas Chemical Co., Ltd.). A compound having two ethylenically unsaturated double bond groups in the molecule. 50 wt% solids PGMEA solution.

“BP-4EAL”: “Light Acrylate” (registered trademark) BP-4EAL (manufactured by Kyoeisha Kagaku Co., Ltd.). A compound having two ethylenically unsaturated double bond groups in the molecule. Solid content 100% by weight.

“Photopolymerization initiator 1”: Compound represented by formula (21). It is the same compound as the compound represented by structural formula (31) described in Patent Document 1 (International Publication No. 2021/111860).

“MEK-ST-40”: Silica particle dispersion liquid containing silica particles with a primary particle diameter distribution of 10 to 15 nm and an aspect ratio of 1.0 to 1.1, and an average primary particle diameter of 12 nm (Nissan Chemical Co., Ltd. )my). The content of silica particles is 40% by weight, the solid content is 40% by weight, and the solvent species is methyl ethyl ketone.

“HMOM-TPHAP”: Compound represented by formula (17) (manufactured by Honshu Kagaku Kogyo Co., Ltd.)

(Synthesis Example 1: Synthesis of hydroxyl group-containing diamine compound A)

18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and incubated at -15°C. Cooled. A solution of 0.11 mol (20.4 g) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise here. 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 filtered and dried under vacuum at 50°C. 30 g of solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced using a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon was no longer deflated and the reaction was terminated. After completion of the reaction, it was filtered to remove the palladium compound as a catalyst, and concentrated with a rotary evaporator to obtain hydroxyl group-containing diamine compound A represented by formula (22).

(Synthesis Example 2: Synthesis of alkali-soluble polyimide precursor A)

Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was mixed with 500 g of N-methylpyrrolidone (hereinafter referred to as "NMP") as a solvent. Abbreviated.) was dissolved in. Here, 45.35 g (0.075 mol) of hydroxyl group-containing diamine compound A obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to 50 g of NMP. was added together with and reacted at 20°C for 1 hour, followed by reaction at 50°C for 2 hours. As an end capping agent, 4.36 g (0.04 mol) of 4-aminophenol was added along with 5 g of NMP, and reacted at 50°C for 2 hours. After that, 50 g of 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal was added. After addition, it was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 3 L of water to obtain a white precipitate. The white precipitate obtained by repeating the above operation 5 times was collected as a residue, washed with water 5 times, and dried in a vacuum dryer at 80°C for 24 hours to obtain alkali-soluble polyimide precursor A. Alkali-soluble polyimide precursor A is a powder with a solid content of 100% by weight, has a weight average molecular weight (Mw) of 25,000, and is a resin having a structural unit represented by formula (11).

(Synthesis Example 3: Synthesis of alkali-soluble polyimide B)

Under a dry nitrogen stream, 58.60 g (0.16 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 8.73 g (0.08 mol) of 3-aminophenol as an end cap, Dissolved in 300.00 g of NMP. Here, 62.04 g (0.20 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride was added along with 100.00 g of NMP, stirred at 20°C for 1 hour, and then stirred at 50°C. It was stirred at ℃ 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 stirring was completed, the solution was added to 5L of water and the white precipitate was collected. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain alkali-soluble polyimide B. Alkali-soluble polyimide B is a resin with a solid content of 100% by weight in powder form, a weight average molecular weight (Mw) of 28,000, and a structural unit represented by formula (10).

(Synthesis Example 4: Synthesis of quinonediazide compound C)

Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (manufactured by Honshu Kagaku Kogyo Co., Ltd.), 36.27 g (0.135 mol) of 5-naphthoquinone diazidesulfonylic acid chloride, 450 g of 1, It was dissolved in 4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine dissolved in 50.00 g of 1,4-dioxane was added dropwise so that the temperature inside the system was 35°C or lower. After dropping, it was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. Afterwards, filtration was performed and the precipitated precipitate was collected. This precipitate was dried with a vacuum dryer to obtain quinonediazide compound C represented by formula (23).

In formula (23), * represents a bonding site with an oxygen atom.

(Synthesis Example 5: Synthesis of alkali-soluble methacrylic resin solution D)

65.07 g of 2-hydroxyethyl methacrylate (0.50 mol), 211.45 g of benzyl methacrylate (1.20 mol), 25.83 g of methacrylic acid (0.30 mol), and 5.00 g of 2 as a thermal polymerization initiator. A mixed solution of 2'-azobis(isobutyronitrile) and 200.00 g of PGMEA was prepared. This was added dropwise over 1 hour using a funnel into 261.02 g of PGMEA that was being stirred while maintaining the liquid temperature at 90°C under a dry nitrogen stream. Thereafter, the solution was heated and maintained at 120°C, and copolymerized with stirring until the weight average molecular weight (Mw) of the finally obtained copolymer reached 8000 to obtain a resin solution. After cooling this to 25°C, it was diluted to a solid content of 30% by weight using PGMEA to obtain alkali-soluble methacrylic resin solution D. Alkali-soluble methacrylic resin solution D is a PGMEA solution containing a copolymer in a mol% ratio of 2-hydroxyethyl methacrylate/benzyl methacrylate/methacrylic acid = 25/60/15.

(Synthesis Example 6: Synthesis of alkali-soluble acrylic resin solution E)

In 260.83 g of PGMEA being stirred and maintained at a liquid temperature of 120°C under a dry nitrogen stream, 72.10 g of 4-hydroxybutylacrylate (0.50 mol) and 92.15 g of 2-ethylhexyl acrylate ( 0.50 mol), 1.47 g of acrylic acid (0.02 mol), and 8.16 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were added dropwise over 1 hour, and the weight average of the copolymer finally obtained was It was stirred at 120°C until the molecular weight reached 10000, and copolymerized to obtain a resin solution. After cooling this to 25°C, it was diluted to a solid content of 30% by weight using PGMEA to obtain alkali-soluble acrylic resin solution E. The alkali-soluble acrylic resin solution E is a PGMEA solution containing a copolymer in a mol% ratio of 4-hydroxybutylacrylate:2-ethylhexyl acrylate:acrylic acid = 49:49:2.

(Synthesis Example 7: Synthesis of fluorene acrylate solution F)

Into the flask, 400.00 g of methyl isobutyl ketone as a solvent was added, 350.00 g of 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene, and 112.10 g of acrylic acid were polymerized. 1.50 g of methoquinone as an inhibitor and 0.30 g of tetraethylammonium bromide as a catalyst were added, and the liquid temperature was maintained at 120°C and stirred for 10 hours to react, then heating was stopped and cooled to room temperature. The reactant was washed with water through a liquid separation operation and dried under reduced pressure to obtain fluorene acrylate (compound represented by formula (24):compound represented by formula (25) = mol% ratio 91:9). Next, PGMEA was added and stirred so that the solid content would be 30% by weight, and fluorene acrylate solution F was obtained.

(Synthesis Example 8: Synthesis of fluorene acrylate solution G)

Into the flask, 200.00 g of PGMEA was added, 275.33 g (0.50 mol) of a fluorene compound represented by formula (26) (manufactured by Osaka Gas Chemical Co., Ltd.), 72.06 g of acrylic acid (1.00 mol), and , 0.50 g of methoquinone and 0.15 g of tetraethylammonium bromide were added, and the liquid temperature was maintained at 100°C and stirred for 2 hours. Next, the liquid temperature was raised to 120°C and stirred for 10 hours to cause reaction.

Additionally, 96.10 g (0.25 mol) of acid dianhydride represented by formula (27), synthesized based on Example 1 of International Publication No. 2011/099518, was added and stirred for 5 hours to react. 30.43 g (0.20 mol) of 1,2,3,6-tetrahydrophthalic anhydride was added and stirred at 90°C for 5 hours, then heating was stopped and cooled to room temperature.

Next, PGMEA was added and stirred so that the solid content was 30% by weight, and fluorene acrylate solution G containing alkali-soluble epoxy acrylate having a structural unit represented by formula (28) was obtained.

In formula (28), * represents the binding site.

(Preparation Example 1: Preparation of pigment dispersion 1)

37.50 g of pigment dispersant 1 and 53.57 g of ZCR-1569H (solid content 70.00% by weight) were mixed with 783.93 g of PGMEA as a solvent and stirred for 10 minutes, then 125.00 g of benzodifuranone-based black pigment A was added. It was stirred for 30 minutes to obtain a preliminary stirred solution. The pre-stirred liquid was fed through a bead mill filled with 0.4 mmϕ zirconia beads ("Toray Ceram" (registered trademark) manufactured by Toray Industries, Ltd.), and wet media dispersion treatment was performed in a circulation manner for 30 minutes. Additionally, the liquid is fed into a bead mill filled with 0.05 mmϕ zirconia beads (“Toray Ceram” (registered trademark) manufactured by Toray Co., Ltd.), and cycled until the cumulative 50% particle size in the particle size distribution of the pigment reaches 99 nm. Wet media dispersion treatment was performed in the following manner to obtain pigment dispersion 1 with a solid content of 20.00% by weight. Table 1 shows the blended weight (g), cumulative 50% particle diameter, and maximum particle diameter of each raw material. In addition, the cumulative 50% particle diameter and maximum particle diameter were obtained by measuring 99.90 g of PGMEA in each 0.10 g of pigment dispersion sampled at each dispersion time using a particle size distribution measuring device "SZ-100" (manufactured by Horiba Seisakusho Co., Ltd.). What was added and diluted was set as a measurement sample, and the cumulative 50% particle diameter was automatically output to determine the end point of the wet media dispersion treatment. In addition, in terms of particle size distribution, the largest particle diameter detected was taken as the maximum particle diameter.

[Table 1]

(Preparation Example 2: Preparation of pigment dispersion 2)

Wet media dispersion treatment was performed in the same manner as in Production Example 1 except that the dispersion time was extended in a cyclic manner until the cumulative 50% particle diameter in the particle size distribution of the pigment reached 60 nm, and a pigment with a solid content of 20.00% by weight was obtained. Dispersion 2 was obtained. Table 1 shows the blended weight (g), cumulative 50% particle diameter, and maximum particle diameter of each raw material.

(Preparation Example 3: Preparation of pigment dispersion 3)

Instead of benzodifuranone-based black pigment A, C. I. Pigment Red 179 was used, and the dispersion time was extended in a cyclic manner until the cumulative 50% particle diameter in the pigment particle size distribution reached 60 nm. Wet media dispersion treatment was performed in the same manner as in Production Example 1, and pigment dispersion 3 with a solid content of 20.00% by weight was obtained. Table 1 shows the blended weight (g), cumulative 50% particle diameter, and maximum particle diameter of each raw material.

(Preparation Example 4: Preparation of pigment dispersion 4)

Instead of the benzodifuranone-based black pigment A, C.I. Pigment Violet 29 was used, and the dispersion time was extended in a cyclic manner until the cumulative 50% particle diameter in the particle size distribution of the pigment reached 60 nm. Wet media dispersion treatment was performed in the same manner as in Production Example 1, and pigment dispersion 4 with a solid content of 20.00% by weight was obtained. Table 1 shows the blended weight (g), cumulative 50% particle diameter, and maximum particle diameter of each raw material.

(Preparation Example 5: Preparation of pigment dispersion 5)

(a) Preparation of perylene-based dark purple pigment B

1,000.00 g of "Spectrasense (registered trademark)" Black K0087 (manufactured by BASF) is heated in an oven at 250°C under atmospheric pressure/air for 1 hour, cooled to room temperature, dried and agglomerated using a ball mill to obtain a dark purple pigment. got it

500.00 g of dark purple pigment, 2.5 kg of friction material (sodium chloride particles), and 250.00 g of dipropylene glycol were mixed, poured into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 90°C for 8 hours. This kneaded product was poured into 5 L of warm water, stirred for 1 hour while maintaining the temperature at 70°C to form a slurry, and filtered and washed repeatedly to remove the grinding material and dipropylene glycol. In addition, after drying in an oven at 100°C under atmospheric pressure/air for 6 hours, the dried agglomerates were broken using a ball mill, and the 3,4,9,10-perylenetetracarboxylic acid bisbenzoimidazole, represented by formula (5), was dried in an oven at 100°C under atmospheric pressure/air for 6 hours. A perylene-based dark purple pigment B consisting of a compound and an isomer mixture of the compound represented by formula (6) was obtained.

(b) Preparation of perylene-based pigment dispersant C

50.00 g of C.I. Pigment Red 178, a perylene-based organic pigment, was dissolved in 500.00 g of 80% by weight concentrated sulfuric acid, heated, and stirred at a liquid temperature of 70°C for 6 hours to proceed with the sulfonation reaction. Next, it was poured into 5 kg of ice water to obtain a slurry containing precipitates and filtered. Next, the residue was washed with ethanol, then washed with water, and dried at 80°C under reduced pressure for 24 hours. Additionally, dry grinding was performed using a nanojetmizer (manufactured by Aisin Nanotechnology Co., Ltd.) to obtain a perylene-based dye-type dispersant C represented by formula (29), which is a mixture of monosulfonic acid, disulfonic acid, and trisulfonic acid. .

(c) Preparation of pigment dispersion 5

Perylene-based dark purple pigment B, perylene-based pigment-type dispersant C, and fluorene acrylate solution G as the dispersion resin were used, and wet media dispersion treatment was carried out in the same manner as in Production Example 1, except that the mixing amounts of each raw material shown in Table 1 were used. This was performed to obtain pigment dispersion 5 with a solid content of 20.00% by weight. The cumulative 50% particle diameter and maximum particle diameter are shown in Table 1.

(Preparation Example 6: Preparation of pigment dispersion 6)

Wet media dispersion treatment was attempted in the same manner as Preparation Example 1 except that perylene-based dark purple pigment B was used instead of benzodifuranone-based black pigment A, but the cumulative 50% particle size in the particle size distribution of the pigment did not reach 99 nm. Pigment dispersion 6 could not be obtained because a significant increase in viscosity occurred before, which increased the pump internal pressure and made it difficult to feed the liquid to the bead mill. Table 1 shows the mixing amount of each raw material.

(Preparation Example 7: Preparation of pigment dispersion 7)

To 721.78 g of mixed solvent (PGME:PGMEA = weight ratio 20:80), 142.22 g of an acrylic dispersant, "DISPERBYK (registered trademark)" 2001 (manufactured by Big Chemi Japan Co., Ltd.; solid content 45% by weight solution) was added. Stirred for 10 minutes. Next, 94.00 g of C.I. Pigment Green 59 (manufactured by DIC Corporation) and 42.00 g of C.I. Pigment Yellow 150 (manufactured by LANXESS) were mixed and stirred for 30 minutes to obtain a preliminary stirred liquid. The pre-stirred liquid was fed through a bead mill filled with 0.4 mm ϕ zirconia beads (“Toray Ceram” (registered trademark) manufactured by Toray Co., Ltd.), and wet media dispersion treatment was performed in a 5-hour circulation method to obtain a pigment with a solid content of 20.00% by weight. Dispersion 7 was obtained.

(Preparation Example 1: Preparation of positive photosensitive composition 1)

Light yellow, 7.50 g of alkali-soluble polyimide precursor A, 2.25 g of quinonediazide compound C in 85.00 g of mixed solvent (PGME: ethyl lactate: γ-butyrolactone = weight ratio 50:40:10). , 5.25 g of HMOM-TPHAP, a thermal crosslinking agent, was added, stirred for 30 minutes to dissolve, and positive photosensitive composition 1 with a solid content of 15.00% by weight was obtained. The combined weight of each raw material is shown in Table 2.

[Table 2]

(Preparation Examples 2 to 3: Preparation of positive photosensitive compositions 2 to 3)

Positive photosensitive compositions 2 to 3 were prepared in the same manner as Preparation Example 1, except that alkali soluble polyimide B or TR4020G (manufactured by Asahi Yukizai Co., Ltd.), an alkali soluble phenolic resin, was used instead of alkali soluble polyimide precursor A. It was prepared. The combined weight of each raw material is shown in Table 2.

(Preparation Example 4: Preparation of negative photosensitive composition 1)

In a yellowish colored solvent mixture of 8.50 g of MBA and 43.03 g of PGMEA, 0.60 g of photopolymerization initiator 1 was added and stirred for 3 minutes to dissolve. To this, 3.15 g of ZCR-1569H and 10.00 g of alkali-soluble methacrylic resin solution D were added. Next, 0.75 g of DPCA-60 (Nippon Kayaku Co., Ltd.) and 3.90 g of EA-0250P (PGMEA solution with a solid content of 50% by weight, manufactured by Osaka Gas Chemical Co., Ltd.) were added. Additionally, 0.60 g of TEPIC-L (manufactured by Nissan Chemical Industries, Ltd.), a thermal crosslinking agent, was added and stirred for 10 minutes to obtain a preparation solution. This preparation liquid and 29.48 g of pigment dispersion liquid 1 were mixed and stirred for 30 minutes to obtain negative photosensitive composition 1 with a solid content of 15.00% by weight. The mixing amount (g) of each raw material is shown in Table 3.

[Table 3]

(Preparation Example 5: Preparation of negative photosensitive composition 2)

In a yellow-light mixed solvent of 4.25 g of MBA and 42.21 g of PGMEA, 0.60 g of NCI-831E was added and stirred for 3 minutes to dissolve. To this, 4.29 g of ZCR-1569H and 2.00 g of alkali-soluble acrylic resin solution E were added. Next, 0.75 g of DPCA-20, 2.40 g of EA-0250P, and 0.75 g of "Light Acrylate" (registered trademark) BP-4EAL (manufactured by Kyoeisha Chemical Co., Ltd.) were added. Additionally, 3.00 g of PGMEA solution with a solid content of 5% by weight of Emulgen A-60 was added and stirred for 10 minutes to obtain a preparation solution. This preparation liquid and 39.75 g of pigment dispersion liquid 1 were mixed and stirred for 30 minutes to obtain negative photosensitive composition 2 with a solid content of 15.00% by weight. The mixing amount (g) of each raw material is shown in Table 3. In addition, the 5% by weight PGMEA solution of Emulgen A-60 is prepared by dissolving 5 parts by weight of “Emugen” (registered trademark) A-60 (manufactured by Kao Co., Ltd.), a nonionic surfactant, in 95 parts by weight of PGMEA. It was prepared as ordered.

(Preparation Example 6: Preparation of negative photosensitive composition 3)

Light yellow, 0.60 g of "Irgacure" (registered trademark) OXE03 ("OXE03" in Table 4), a photopolymerization initiator, was added to a mixed solvent of 8.50 g of MBA and 39.94 g of PGMEA, and stirred for 3 minutes to dissolve. To this, 11.00 g of alkali-soluble methacrylic resin solution D and 1.60 g of TR4020G, which is an alkali-soluble phenol resin, were added. Next, 0.75 g of DPCA-60, 7.50 g of fluorene acrylate solution F, and 0.60 g of TEPIC-L were added. Additionally, 0.03 g of a 5% by weight PGMEA solution of BYK-333 (manufactured by Big Chemi Japan Co., Ltd.), a silicone-based leveling agent, was added and stirred for 10 minutes to obtain a preparation solution. This preparation liquid and 29.48 g of pigment dispersion liquid 2 were mixed and stirred for 30 minutes to obtain negative photosensitive composition 3 with a solid content of 15.00% by weight. The mixing amount (g) of each raw material is shown in Table 4.

[Table 4]

(Preparation Examples 7 to 9: Preparation of negative photosensitive compositions 4 to 6)

In addition, except that MEK-ST-40 or pigment dispersion 3 to 4 was used, negative photosensitive composition 4 to 4 with a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 6, with the mixing amount (g) of each raw material shown in Table 4. Got 6.

(Preparation Example 10: Preparation of negative photosensitive composition 7)

Light yellow, in 67.55 g of mixed solvent (PGME:PGMEA:γ-butyrolactone = weight ratio 30:60:10), 1.20 g of C.I. Solvent Blue 97, an anthraquinone dye, and 0.60 g of methine dye. C. I. Solvent Yellow 93 and 1.20 g of C. I. Acid Red 52, a xanthene dye, were added and stirred for 2 hours. Next, 0.60 g of “Irgacure” (registered trademark) OXE03 (“OXE03” in Table 5) was added and stirred for 3 minutes to dissolve. To this, 1.71 g of ZCR-1569H, 16.65 g of alkali-soluble methacrylic resin solution D, and 1.60 g of TR4020G were added. Next, 0.75 g of DPCA-60, 7.50 g of fluorene acrylate solution F, and 0.60 g of TEPIC-L were added. Additionally, 0.03 g of a 5% by weight PGMEA solution of BYK-333, a silicone-based leveling agent, was added and stirred for 30 minutes to obtain negative photosensitive composition 7 with a solid content of 15.00% by weight. The mixing amount (g) of each raw material is shown in Table 5.

[Table 5]

(Preparation Example 11: Preparation of negative photosensitive composition 8)

Negative photosensitive composition 8 with a solid content of 15.00% by weight in the same manner as Preparation Example 4 except that alkali-soluble polyimide B was used instead of alkali-soluble methacrylic resin solution D, with the mixing amount (g) of each raw material shown in Table 6. got it

[Table 6]

(Preparation Example 12: Preparation of negative photosensitive composition 9)

In the same manner as Preparation Example 4 except that Pigment Dispersion 1 and EA-0250P were not used, Negative Photosensitive Composition 9 with a solid content of 15.00% by weight was obtained with the mixing amount (g) of each raw material shown in Table 6.

(Preparation Example 13: Preparation of negative photosensitive composition 10)

In the same manner as Preparation Example 4, except that Pigment Dispersion 5 was used instead of Pigment Dispersion 1 and fluorene acrylate solution F was used instead of EA-0250P, the mixing amount (g) of each raw material shown in Table 6 was used, and the solid content was 15.00. A negative photosensitive composition 10% by weight was obtained.

(Preparation Example 14: Preparation of negative photosensitive green composition for color filter)

0.60 g of "Irgacure" (registered trademark) OXE03 was added to 34.26 g of yellowish mixed solvent (PGME:PGMEA = weight ratio 20:80) and stirred for 5 minutes to dissolve. Additionally, 31.71 g of alkali-soluble methacrylic resin solution D and 4.00 g of DPCA-60 were added and stirred for 10 minutes to obtain a prepared solution. This mixture and 29.43 g of pigment dispersion 7 were mixed and stirred for 30 minutes to obtain a negative photosensitive green composition for color filters with a solid content of 20.00% by weight.

(Example 1)

Negative photosensitive composition 1 was applied to the surface of a transparent glass substrate, “Tempax” (manufactured by AGC Techno Glass Co., Ltd.), using a spin coater, adjusting the rotation speed so that the film thickness of the final cured film obtained was 1.5 μm. A coating film was obtained. The coating film was prebaked at 110°C under atmospheric pressure for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Co., Ltd.) to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, the entire surface of the prebaked film was irradiated with the g, h, i mixing line of an ultra-high pressure mercury lamp at the optimal exposure amount (A) determined by the above-described method to obtain an exposed film. Next, development, rinsing, and drying were performed in the same manner as when measuring the optimal exposure amount (A), and a solid developed film was obtained. Using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developing film was heated at 250°C for 1 hour in an air atmosphere, and a solid-shaped cured film with a film thickness of 1.5 μm was obtained. A substrate for density evaluation was obtained, and the optical density (OD/μm) per 1.0 μm film thickness of the cured product of negative photosensitive composition 1 was evaluated by the method described above.

Next, the same method was used except that positive photosensitive composition 1 was used instead of negative photosensitive composition 1, no exposure was performed, and the development time was the same as when measuring the optimal exposure amount (B) described above, and a film thickness of 1.5 μm was obtained. A substrate for optical density evaluation having a solid cured film was obtained, and the optical density per 1.0 μm film thickness (OD/μm) of the cured product of positive photosensitive composition 1 was evaluated by the method described above. The evaluation results are shown in Table 7. In addition, a substrate on which a copper cured film was produced on a silicon wafer instead of a transparent glass substrate was analyzed with an infrared absorption spectrum, and it was confirmed that the cured product of positive photosensitive composition 1 had an imide bond and a benzoxazole skeleton.

Additionally, an organic EL display device including a pixel split layer was produced by the following method. Figure 11 shows the manufacturing process of the organic EL display device, including the forming process of the pixel split layer.

Positive photosensitive composition 1 was applied to the surface of an alkali-free glass substrate 55 of 100 mm in length and 100 mm in width using a spin coater and adjusting the rotation speed so that the final thickness of the planarization layer obtained was 1.0 μm. , a coating film was obtained. Additionally, the coating film was prebaked at 110°C under atmospheric pressure for 120 seconds using a hot plate to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, a pattern is patterned on the prebaked film at an exposure dose of 100 mJ/cm2 through a positive square pattern exposure mask (one square light-shielding portion of 30 mm in height and 30 mm in width is provided in the center). By exposure, an exposure film was obtained. The exposed film was developed for 60 seconds using a 2.38% by weight TMAH aqueous solution, rinsed for 30 seconds using deionized water, and then dried with air blow to obtain a developed film in a pattern shape. Using a high-temperature inert gas oven, the developing film was heated at 250°C in an air atmosphere for 1 hour to obtain a square flattening layer 56 with a vertical width of 30 mm and a horizontal width of 30 mm.

Next, a silver alloy (an alloy consisting of 99.00% by weight silver and 1.00% by weight copper) was deposited on the entire surface by a sputtering method. The patterned cured film of positive photosensitive composition 3 was used as a resist film for etching, and was immersed and etched in silver alloy etchant SEA-1 at a liquid temperature of 30°C to obtain a patterned silver alloy film with a film thickness of 50 nm. Additionally, an ITO film was formed on the entire surface by sputtering. Positive photosensitive composition 3 was used as a resist film, immersed in a 5% by weight aqueous oxalic acid solution at a liquid temperature of 50°C for 5 minutes, shower washed with deionized water for 2 minutes, and dried with an air blow to form a copper patterned film with a film thickness of 10 nm. An ITO membrane was obtained. Through the above steps, a first electrode formation substrate provided with a first electrode 57 made of a lamination pattern of a silver alloy film and an ITO film was obtained.

Negative photosensitive composition 1 was applied to the surface of the first electrode forming substrate using a spin coater, adjusting the rotation speed so that the film thickness of the finally obtained layer (A) was 1.5 μm, to obtain a coating film. Additionally, using a hot plate, the coating film was prebaked at 110°C under atmospheric pressure for 120 seconds to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, a negative square pattern exposure mask (1000 square light-shielding portions with a vertical width of 7.0 ㎛ and a horizontal width of 7.0 ㎛ arranged) is applied to the optimal exposure amount (A) obtained by the method described above. A pattern exposure was performed on the prebaked film to obtain an exposed film. In addition, pattern exposure was performed by bringing a negative square pattern exposure mask into contact with the surface of the prebake film. Next, development, rinsing, and drying were performed in the same manner as the measurement of the optimal exposure amount (A), and a developed film in a pattern shape was obtained. Using a high-temperature inert gas oven, the developing film was heated at 250° C. in an air atmosphere for 1 hour to obtain a layer (A) with a film thickness of 1.5 μm containing the cured product of the negative photosensitive composition 1.

Positive photosensitive composition 1 was applied to the surface of the layer (B) using a spin coater, adjusting the rotation speed so that the final thickness of the layer (B) obtained was 0.3 μm, and a coating film was obtained. Additionally, using a hot plate, the coating film was prebaked at 110°C under atmospheric pressure for 120 seconds to obtain a prebaked film. A near-infrared camera is used to align the position of the positive square pattern exposure mask, and a double-sided alignment single-sided exposure device is used through the positive square pattern exposure mask (1,000 square transparent parts with a vertical width of 7.0 μm and a width of 7.0 μm arranged). Using , a pattern was exposed to the prebaked film with the optimal exposure amount (B) determined by the above-described method to obtain an exposed film. In addition, pattern exposure was performed by bringing a positive square pattern exposure mask into contact with the surface of the prebake film. Next, development, rinsing, and drying were performed in the same manner as the measurement of the optimal exposure amount (B), and a developed film in a pattern shape was obtained. Using a high-temperature inert gas oven, the developing film was heated at 250° C. in an air atmosphere for 1 hour to obtain a layer (B) with a film thickness of 0.3 μm containing the cured product of positive photosensitive composition 1.

From the above, the pixel division layer has 1000 openings with an opening width of 7.0 μm in an area of 30 mm in height and 30 mm in width at the center of the first electrode forming substrate, and the layer (B) is disposed on the surface of the layer (A). A pixel split layer forming substrate provided with (58) was obtained. In the portion of the pixel division layer 58 where the layer (B) is disposed on the surface of the layer (A), the maximum film thickness of the layer (A) is 1.5 μm, and the maximum film thickness of the layer (B) is 1.5 μm. The value was 0.3㎛. The area ratio that layer (B) covered the surface of layer (A) was 100% of 100% of the total surface area of layer (A) (FIG. 3). In addition, for the non-formed portion of the second electrode 60 described later, the film thickness after forming the layer (A) and the film thickness after forming the layer (B) were measured using a stylus type film thickness measuring device (Tokyo Seimitsu Co., Ltd.). ; The film thickness of layer (A) and the film thickness of layer (B) are calculated by rounding off the two decimal places of the average value measured at three locations in each surface using a surfcom. It was taken as the sum of . The value obtained by subtracting the film thickness of layer (A) from the total value of the film thickness of layer (A) and the film thickness of layer (B) was taken as the film thickness of layer (B). Separately, among the film thicknesses measured at three locations in the above-mentioned surface, the value obtained by rounding off the maximum value to two decimal places was taken as the maximum film thickness of the layer (A). In addition, the value obtained by subtracting the minimum value of the film thickness of layer (A) from the maximum value of the sum of the film thickness of layer (A) and the film thickness of layer (B), rounded to two decimal places, is calculated as layer (B). was set to the maximum value.

Next, in order to form the organic EL layer 59 including the light-emitting layer in the opening of the pixel division layer 58 by vacuum deposition, pixels are divided with respect to the deposition source under deposition conditions of a vacuum degree of 1 × 10 ^-3 Pa or less. The layer forming substrate was rotated, and first, the compound (HT-1) represented by formula (30) as a hole injection layer was deposited to a thickness of 50 nm, and the compound (HT-2) represented by formula (31) as a hole transport layer was formed to a film thickness of 50 nm. did. Next, on the light emitting layer, a compound (GH-1) represented by formula (32) as a host material and a compound (GD-1) represented by formula (33) as a dopant material were deposited at a film thickness of 40 nm. Next, as an electron transport material, a compound (ET-1) represented by formula (34) and a compound (LiQ) represented by formula (35) were laminated at a volume ratio of 1:1 and a film thickness of 40 nm.

Next, after depositing 2 nm of a compound (LiQ), an alloy of silver and magnesium (volume ratio 10:1) was deposited to a film thickness of 150 nm to form the second electrode 60. Next, under a low humidity/nitrogen atmosphere, an epoxy resin adhesive was used to seal the cap-shaped glass plate by adhering it to obtain an organic EL display device in which green light-emitting pixels were arranged. In addition, since the layers constituting the organic EL layer 59 are very thin compared to the above-mentioned pixel division layer, each was measured using a crystal oscillation type film thickness monitor suitable for thin films of less than 100 nm, and the thickness of three points in the plane was measured. The value obtained by rounding off the average value to two decimal places was taken as the film thickness.

The luminescence reliability (high-temperature continuous driving test) of the organic EL display device manufactured through the above procedure was evaluated by the method described above. The evaluation results are shown in Table 7-1 and Table 7-2.

[Table 7-1]

[Table 7-2]

(Example 2)

The optical density (OD/μm) of the cured film and the luminescence reliability (high temperature continuous driving test) of the organic EL display device were evaluated in the same manner as in Example 1, except that negative photosensitive composition 3 was used instead of negative photosensitive composition 1. The evaluation results are shown in Table 7-1 and Table 7-2.

(Examples 3 to 4)

The optical density (OD/㎛) of the cured film was measured in the same manner as in Example 1, except that negative photosensitive composition 3 was used instead of negative photosensitive composition 1, and positive photosensitive compositions 2 to 3 were used instead of positive photosensitive composition 1. and the luminescence reliability (high-temperature continuous driving test) of the organic EL display device was evaluated. The evaluation results are shown in Table 7-1 and Table 7-2.

(Examples 5 to 8)

The optical density (OD/㎛) of the cured film and the luminescence reliability (high temperature continuous driving test) of the organic EL display device were tested in the same manner as in Example 1, except that negative photosensitive compositions 4 to 7 were used instead of negative photosensitive composition 1. evaluated. The evaluation results are shown in Table 7-1, Table 7-2, Table 8-1, and Table 8-2.

[Table 8-1]

[Table 8-2]

(Example 9)

Negative photosensitive composition 4 was used instead of negative photosensitive composition 1, and the area ratio of the layer (B) with a film thickness of 1.5 μm covering the surface of the layer (A) with a film thickness of 1.5 μm was the entire layer (A). It is formed to cover 20% of 100% of the surface area, and a photo-spacer function is provided to the pixel division layer (FIG. 4). In forming the layer (B), a positive square pattern exposure mask (height width: 7.0 ㎛, width: The same method as Example 5 except that a positive square pattern exposure mask (500 square transparent parts with a vertical width of 20.0 μm and a horizontal width of 20.0 μm was arranged) was used instead of 1000 square transparent parts of 7.0 μm. An organic EL display device was produced using this method, and luminescence reliability (high-temperature continuous driving test) was evaluated. The evaluation results are shown in Table 8-1 and Table 8-2. Additionally, in the area where layer (B) was disposed on the surface of layer (A), the maximum value of the film thickness of layer (A) was 1.5 μm, and the maximum value of the film thickness of layer (B) was 1.5 μm.

(Example 10)

An organic EL display device was manufactured in the same manner as in Example 9 except that negative photosensitive composition 5 was used instead of negative photosensitive composition 4, and luminescence reliability (high temperature continuous driving test) was evaluated. The evaluation results are shown in Table 8-1 and Table 8-2.

(Example 11)

The optical density (OD/μm) of the cured film and the luminescence reliability (high temperature continuous driving test) of the organic EL display device were evaluated in the same manner as in Example 1, except that negative photosensitive composition 10 was used instead of negative photosensitive composition 1. The evaluation results are shown in Table 8-1 and Table 8-2.

(Comparative Example 1)

An organic EL display device was manufactured in the same manner as in Example 1 except that the layer (B) was not formed, and the luminescence reliability (high temperature continuous driving test) was evaluated. The evaluation results are shown in Table 9-1 and Table 9-2.

[Table 9-1]

[Table 9-2]

(Comparative Example 2)

Examples except that layer (A) was formed using positive photosensitive composition 1 instead of negative photosensitive composition 1, and layer (B) was formed using negative photosensitive composition 1 instead of positive photosensitive composition 1. An organic EL display device was manufactured in the same manner as in 1, and luminescence reliability (high temperature continuous driving test) was evaluated. The evaluation results are shown in Table 9-1 and Table 9-2. The pixel division layer provided in the organic EL display device produced in Comparative Example 2 is a pigment and an ethylenic acid on the surface of the layer (A) containing the cured product of positive photosensitive composition 1 containing a resin and a photoacid generator. It is a pixel dividing layer in which a layer (B) containing a cured product of negative photosensitive composition 1 containing a compound having two or more unsaturated double bond groups in the molecule and a photopolymerization initiator is disposed. Additionally, the maximum film thickness of layer (A) was 0.3 ㎛, and the maximum film thickness of layer (B) was 1.5 ㎛.

(Comparative Example 3)

An attempt was made to form the layer (A) in the same manner as in Example 1 using negative photosensitive composition 2 instead of negative photosensitive composition 1, but due to insufficient resolution, the aperture width was 7.0 ± 0.1 μm in measurement of the optimal exposure amount (A). It was not possible to form an opening. Therefore, an organic EL display device could not be manufactured.

(Comparative Example 4)

An organic EL display device was manufactured in the same manner as in Example 1 except that the layer (B) was formed using negative photosensitive composition 1 instead of positive photosensitive composition 1, and luminescence reliability (high temperature continuous driving test) was evaluated. . The evaluation results are shown in Table 9-1 and Table 9-2.

(Comparative Example 5)

An organic EL display device was manufactured in the same manner as in Example 1 except that the layer (A) was formed using the negative photosensitive composition 8 instead of the negative photosensitive composition 1 and the layer (B) was not formed, and the luminescence reliability was tested. (High temperature continuous driving test) was evaluated. The evaluation results are shown in Table 9-1 and Table 9-2.

(Comparative Example 6)

An organic EL display device was manufactured in the same manner as in Example 1 except that the layer (B) was formed using negative photosensitive composition 9 instead of positive photosensitive composition 1, and luminescence reliability (high temperature continuous driving test) was evaluated. . The evaluation results are shown in Table 10-1 and Table 10-2.

[Table 10-1]

[Table 10-2]

(Comparative Example 7)

An organic EL display device was manufactured in the same manner as in Example 1, except that positive photosensitive composition 3 was used instead of negative photosensitive composition 1 to form the layer (A), and positive photosensitive composition 3 was used instead of positive photosensitive composition 1. was manufactured and the luminescence reliability (high-temperature continuous driving test) was evaluated. The evaluation results are shown in Table 10-1 and Table 10-2.

(Comparative Example 8)

When measuring the optimal exposure dose (A) of the negative photosensitive composition 1 used for forming the layer (A), the g, h, and i mixing lines of an ultra-high pressure mercury lamp were measured from the developer side on the obtained developer film-forming substrate at 1000 mJ (mJ/cm2). : A second exposure process is added to expose the entire surface with an exposure amount of 1000 mJ (mJ/cm2: i-line conversion value) in the same manner when manufacturing a pixel division layer formation substrate. An organic EL display device was manufactured in the same manner as in Example 1 except that a second exposure process was added and the layer (B) was not formed, and the luminescence reliability (high temperature continuous driving test) was evaluated. The evaluation results are shown in Table 10-1 and Table 10-2.

(Comparative Example 9)

Instead of a negative square pattern exposure mask (1,000 square light-shielding portions with a height of 7.0 ㎛ and width of 7.0 ㎛), a low-resolution negative square pattern exposure mask (height of 50.0 ㎛, width of 260.0 ㎛) is used. Measurement of the optimal exposure amount (A) of the negative photosensitive composition 1 used in forming the layer (A) so that an aperture with an aperture width of 50.0 ± 0.1 mu m is obtained using an array of 50 ㎛ rectangular light-shielding portions; An organic EL display device was manufactured in the same manner as in Example 1 except that the pixel split layer formation substrate was manufactured and the layer (B) was not formed, and the luminescence reliability (high temperature continuous driving test) was evaluated. The evaluation results are shown in Table 10-1 and Table 10-2.

(Comparative Example 10)

Instead of a negative square pattern exposure mask (1000 square light-shielding portions of height: 7.0 ㎛, width: 7.0 ㎛ arranged), a low-resolution negative square pattern exposure mask (height: 30.0 ㎛, width: 30.0 ㎛) is used. Measurement of the optimal exposure amount (A) of the negative photosensitive composition 1 used in forming the layer (A) so that an aperture with an aperture width of 30.0 ± 0.1 mu m is obtained using an array of 100 ㎛ rectangular light-shielding portions; An organic EL display device was manufactured in the same manner as in Example 1 except that the pixel split layer formation substrate was manufactured and the layer (B) was not formed, and the luminescence reliability (high temperature continuous driving test) was evaluated. The evaluation results are shown in Table 10-1 and Table 10-2.

(Example 12)

Instead of negative photosensitive composition 1, negative photosensitive composition 4 was used, and instead of the negative square pattern exposure mask (1000 square light-shielding portions with a vertical width of 7.0 μm and a horizontal width of 7.0 μm arranged), a negative hole was used. Optimum exposure amount of negative photosensitive composition 4 used in forming layer (A) using a pattern exposure mask (500 circular light-shielding portions with a diameter of 17.0 μm arranged) so that an opening with an opening width of 17.0 ± 0.1 μm is obtained. The measurement in (A) and the production of the pixel dividing layer forming substrate were performed. Instead of a positive type square pattern exposure mask (1000 square transparent parts with a vertical width of 7.0 μm and a horizontal width of 7.0 μm arranged), a positive type was used. Optimum image of positive photosensitive composition 1 used in forming layer (B) using a hole pattern exposure mask (an array of 500 circularly shaped transparent portions with a diameter of 30.0 ㎛) so that an opening with an opening width of 30.0 ± 0.1 ㎛ is obtained. An organic EL display device was manufactured in the same manner as in Example 1 except that the exposure amount (B) was measured and the pixel split layer formation substrate was fabricated, and the luminescence reliability (high temperature continuous driving test) was evaluated. Additionally, the area ratio that layer (B) covered the surface of layer (A) was 92% of 100% of the total surface area of layer (A). The evaluation results (high temperature continuous operation test) are shown in Table 11-1 and Table 11-2.

[Table 11-1]

[Table 11-2]

(Comparative Example 11)

An organic EL display device was manufactured in the same manner as in Example 12 except that the layer (B) was not formed, and the luminescence reliability (high temperature continuous driving test) was evaluated. The evaluation results are shown in Table 11-1 and Table 11-2.

(Example 13)

An organic EL display device was produced in the same manner as in Example 12 except that the layer (B) was formed to have a film thickness of 0.5 μm, and the luminescence reliability (light fastness test) was evaluated. The evaluation results are shown in Table 12-1 and Table 12-2.

[Table 12-1]

[Table 12-2]

(Comparative Example 12)

An organic EL display device was manufactured in the same manner as in Example 12, except that the layer (B) was formed so that the film thickness was 0.5 μm, and the layer (B) was not formed, and the luminescence reliability (light fastness test) was evaluated. . The evaluation results are shown in Table 12-1 and Table 12-2.

(Example 14)

An organic EL display device was manufactured in the same manner as in Example 12 except that the layer (B) was formed so that the film thickness was 0.5 ㎛, and the color filter substrate manufactured by the following method was optically bonded using an epoxy adhesive. By attaching it to the drawing side, an organic EL display device equipped with a color filter substrate was obtained, and the luminescence reliability (light fastness test) was evaluated. The evaluation results are shown in Table 12-1 and Table 12-2.

<Production of color filter substrate>

A negative photosensitive green composition for color filters was applied to the surface of Tempax, a transparent glass substrate, with a spin coater while adjusting the rotation speed so that the film thickness of the final cured film obtained was 1.0 μm to obtain a coating film. Using a hot plate, the coating film was prebaked at 110°C under atmospheric pressure for 120 seconds to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, the entire surface of the prebake film was exposed to the g, h, and i mixed lines of an ultra-high pressure mercury lamp at an exposure dose of 100 mJ/cm 2 to obtain an exposed film. The substrate on which the exposure film was formed was heated at 230°C for 30 minutes in an air atmosphere using a high-temperature inert gas oven to obtain a green color filter substrate.

(Comparative Example 13)

An organic EL display device including a color filter substrate was produced in the same manner as in Example 14 except that the layer (B) was not formed, and the luminescence reliability (light fastness test) was evaluated. The evaluation results are shown in Table 12-1 and Table 12-2.

(Example 15)

The luminescence reliability (light fastness test) of an organic EL display device equipped with a color filter substrate manufactured in the same manner as in Example 14 was evaluated, except that negative photosensitive composition 10 was used instead of negative photosensitive composition 4. The evaluation results are shown in Table 12-1 and Table 12-2.

(Comparative Example 14)

An organic EL display device including a color filter substrate was produced in the same manner as in Example 15 except that the layer (B) was not formed, and the luminescence reliability (light fastness test) was evaluated. The evaluation results are shown in Table 12-1 and Table 12-2.

From the above results, compared to the organic EL display devices manufactured in Examples 1 to 15, the organic EL display devices manufactured in Comparative Examples 1 to 2 and 4 to 14 had high light blocking properties and had an aperture with a narrow aperture width. It can be seen that excellent light emission reliability is obtained by providing the pixel dividing layer.

Therefore, it can be seen that the organic EL display device of the present invention is useful.

Industrial applicability

The organic EL display device of the present invention can be suitably used in applications requiring high resolution and luminous reliability of the display portion, for example, electronic devices such as small wearable devices of the wristwatch type used outdoors and foldable smartphones. You can.

1: TFT 2: Wiring
3: TFT insulating layer 4: Planarization layer
5: first electrode 6: substrate
7: Contact hole 8: Floor (A)
9: Layer (B) 10: Pixel division layer
11: light-emitting pixel 12: second electrode
13: substrate 14: black matrix
15: Green color filter 16: Red color filter
17: Blue color filter 18: Substrate
19: planarization layer 20: first electrode
21: Floor (A) 22: Floor (B)
23: substrate 24: planarization layer
25: first electrode 26: layer (A)
27: layer (B) 28: substrate
29: planarization layer 30: first electrode
31: Floor (A) 32: Floor (B)
33: substrate 34: planarization layer
35: first electrode 36: layer (A)
37: layer (B) 38: substrate
39: planarization layer 40: first electrode
41: Layer (A) 42: Layer (B)
43: TFT 44: Layer (A)
45: Opening of layer (A) where blue light-emitting pixels are arranged
46: Opening of layer (A) where red light-emitting pixels are arranged
47: Opening of layer (A) where green light-emitting pixels are arranged
48: Floor (A)
49: Opening of layer (A) where blue light-emitting pixels are arranged
50: Opening of layer (A) where red light-emitting pixels are arranged
51: Opening of layer (A) where green light-emitting pixels are arranged
52: Layer (A) 53: Light-emitting region
54: Non-luminous area 55: Alkali-free glass substrate
56: planarization layer 57: first electrode
58: Pixel division layer 59: Organic EL layer
60: second electrode

Claims (11)

An organic EL display device comprising a substrate, a planarization layer, a first electrode, a pixel split layer, a light emitting pixel, and a second electrode in this order, wherein the pixel split layer includes a layer (A) and a layer (B),
The layer (A) is a layer disposed on the surface of the first electrode by partially exposing the surface of the first electrode, and the layer (B) is a layer disposed on at least a portion of the surface of the layer (A). ,
The layer (A) contains a cured product of the negative photosensitive composition (a) containing a pigment and/or dye, a compound having two or more ethylenically unsaturated double bond groups in the molecule, and a photopolymerization initiator, and the layer ( B) An organic EL display device containing a cured product of the positive photosensitive composition (b) containing this resin and a photoacid generator. According to claim 1,
An organic EL display device in which, in the display portion, the area ratio of the layer (B) covering the surface of the layer (A) is 20 to 100% of 100% of the total surface area of the layer (A). The method of claim 1 or 2,
An organic EL display device further comprising a color filter on a light extraction side of the light-emitting pixel. The method of claim 1 or 2,
An organic EL display device, wherein the layer (A) is a display portion and has an opening with an opening area of 30.0 to 260.0 μm ² where the light-emitting pixels are disposed. The method of claim 1 or 2,
An organic EL display device wherein the cured product of the positive photosensitive composition (b) contains a resin having an imide bond and/or a benzoxazole skeleton. The method of claim 1 or 2,
An organic EL display device in which the cured product of the negative photosensitive composition (a) contains the pigment, and the pigment contains a benzodifuranone-based black pigment represented by formula (1) or (2).


(In formulas (1) and (2), R ¹ to R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, or a carboxyl group.) The method of claim 1 or 2,
The cured product of the negative photosensitive composition (a) is CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 190, CI Pigment Violet 29 and 3, An organic EL display device further comprising at least one type of perylene-based organic pigment selected from the group consisting of 4,9,10-perylenetetracarboxylic acid bisbenzimidazole. The method of claim 1 or 2,
An organic EL display device wherein the cured product of the negative photosensitive composition (a) further contains 3,4,9,10-perylenetetracarboxylic acid bisbenzoimidazole. The method of claim 1 or 2,
In the area where the layer (B) is disposed on the surface of the layer (A), the maximum film thickness of the layer (A) is 0.5 to 3.0 μm, and the maximum film thickness of the layer (B) is 0.5 to 3.0 μm. An organic EL display device having a region of 0.1 to 3.0 μm. The method of claim 1 or 2,
An organic EL display device wherein the optical density (OD/μm) per 1 μm film thickness of the layer (A) is 0.5 to 1.5. The method of claim 1 or 2,
An organic EL display device in which the cured product of the negative photosensitive composition (a) contains silica particles having a primary particle diameter of 5 to 30 nm and an aspect ratio (major axis/minor axis) of 1.0 to 1.5.