JP7352176B2 - Photosensitive resin composition, cured film, and display device using the cured film - Google Patents

Description

The present invention relates to a photosensitive resin composition, a cured film, and a display device using the cured film.

Many products using organic electroluminescence (hereinafter referred to as "organic EL") light emitting elements have been developed in display devices having thin displays, such as smartphones, tablet PCs, and televisions. Generally, an organic EL light emitting element has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and between the first electrode and the second electrode facing each other, It can emit light by applying voltage. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as materials for the flattening layer and materials for the insulating layer. Among them, photosensitive resin compositions using polyimide-based or polybenzoxazole-based resins have high heat resistance and generate little gas components from the cured film, so they can provide highly durable organic EL display devices. It is suitably used because it can be used (Patent Document 1).

In recent years, printing methods typified by inkjet methods have come to be used to form light emitting layers. Specifically, for example, after forming a barrier rib pattern on a substrate, a solution of a functional material such as a luminescent material, a hole transport material, an electron transport material, etc. is dropped into the openings between the barrier ribs using an inkjet method. A method of forming an organic EL light emitting device having a functional layer is known.

In order to drop a functional material solution into a predetermined section of a partition pattern using the inkjet method, it is necessary to make the partition pattern liquid repellent. In order to achieve this, a method is being considered in which the upper surface of the partition pattern on the substrate is subjected to fluorination treatment by plasma irradiation to develop liquid repellency (Patent Document 2).

In addition, a method of forming partition walls using a photosensitive resin composition to which a liquid-repellent compound is added has also been studied. For example, resist compositions containing specific fluorine-based polymers (Patent Document 3) and photosensitive resin compositions containing a fluorine-containing compound containing a silane compound and a novolac type phenol resin as main components (Patent Document 4) are being considered. .

Japanese Patent Application Publication No. 2002-91343 Patent No. 4612773 JP2012-220860A Patent No. 6098635

However, demands for high durability such as longer drive life for organic EL light emitting elements are becoming stricter year by year, and even after durability tests under accelerated conditions such as high temperature, high humidity, and light irradiation, the demands for high durability as light emitting elements are becoming stricter. Maintaining performance is required.

Since the technology of Patent Document 1 does not have liquid repellency in the formed partition walls, there is a problem in that the functional material solution dropped by the inkjet method crosses the partition walls and mixes into nearby pixels, causing poor light emission.

The technique disclosed in Patent Document 2 has a problem in that the liquid-repellent component also adheres to the openings between the partition walls due to the fluorination treatment, resulting in insufficient ink wettability at the openings.

In addition, the techniques of Patent Document 3 and Patent Document 4 have sufficient liquid repellency and can be patterned as a photosensitive resin composition, but since the main component resin uses a phenol compound, Display defects are likely to occur due to outgassing components from the resin composition constituting the partition pattern, resulting in the problem of significantly shortening the driving life of the organic EL element.

Therefore, an object of the present invention is to solve the problems associated with the prior art as described above, and to provide a photosensitive resin composition that has excellent ink wettability in the openings and has a cured film with sufficient liquid repellency. do. Another object of the present invention is to provide a display device that includes a cured film of the photosensitive resin composition, has fewer display defects, and has high durability against subsequent heat treatment.

In order to solve the above problems, the present invention has the following configuration. That is,
A first aspect of the photosensitive resin composition of the present invention is a photosensitive resin composition containing a liquid repellent material (A) having at least an amide group or a urethane group, an alkali-soluble resin (B), and a photosensitizer (E). The alkali-soluble resin (B) contains at least one alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.

Moreover, the first aspect of the cured film of the present invention consists of the cured product of the first aspect of the photosensitive resin composition of the present invention.

Further, a first aspect of the display device of the present invention is a display device having a grid-like partition wall formed on a substrate, and the partition wall includes the first embodiment of the cured film of the present invention.

Further, the first embodiment of the method for manufacturing a substrate with partition walls of the present invention includes the following steps (1) to (4) in this order.
(1) Step of applying the first embodiment of the photosensitive resin composition of the present invention on a substrate having a first electrode to form a photosensitive resin film (2) Step of exposing the photosensitive resin film to light (3) Step of developing the exposed photosensitive resin film (4) Step of forming partition walls by heat-treating the developed photosensitive resin film.

Further, the first embodiment of the method for manufacturing a display device of the present invention includes the following steps (5) to (6) in this order.
(5) In a partition-equipped substrate having partition walls containing the cured product of the first embodiment of the photosensitive resin composition of the present invention, a functional ink is applied by an inkjet to the area surrounded by the partition walls to form a functional layer. Step (6) of forming a second electrode on the functional layer.

It is possible to provide a photosensitive resin composition that has excellent ink wettability in the openings and a cured film that has sufficient liquid repellency. Further, the present invention can provide a display device that includes a cured film of the photosensitive resin composition, has fewer display defects, and has high durability against subsequent heat treatment.

This is an example of a cross section of a lattice-shaped partition formed on a substrate, cut perpendicular to the longitudinal direction of the partition and the surface of the substrate. FIG. 2 is a schematic diagram of a substrate used for evaluation in Examples.

Embodiments of the present invention will be described in detail.

A first aspect of the photosensitive resin composition of the present invention is a photosensitive resin composition containing a liquid repellent material (A) having at least an amide group or a urethane group, an alkali-soluble resin (B), and a photosensitizer (E). The alkali-soluble resin (B) contains at least one alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.

The first embodiment of the photosensitive resin composition of the present invention contains a liquid repellent material (A) having at least an amide group or a urethane group in order to impart liquid repellency to the surface of the cured film. In the first embodiment of the photosensitive resin composition of the present invention, "liquid repellent material (A) having at least an amide group or urethane group" is referred to as "component (A)" or "liquid repellent material (A)". May be called. When component (A) has an amide group or urethane group, it improves compatibility with the alkali-soluble resin (B) described later, reduces defects such as repellency, and improves the uniformity of the thickness of the cured film. As a result, display defects of the display device are reduced. In particular, in the first embodiment of the photosensitive resin composition of the present invention, the alkali-soluble resin (B) is selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. Since it contains at least one type of alkali-soluble resin, the effect of significantly improving compatibility can be obtained.

The liquid repellent material (A) having at least an amide group or a urethane group preferably contains a compound having a structural unit represented by the following general formula (1) or the following general formula (11).

In general formula (1), R ¹ , R ² and R ³ represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.

In the general formula (11), R ¹⁸ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and R ¹⁹ represents an aliphatic group having 1 to 6 carbon atoms. A represents a urethane group as shown in (A-1) or (A-2) below.

A compound having a structural unit represented by general formula (1) or general formula (11) is, for example, a (meth)acrylamide monomer represented by the following general formula (3) or a compound represented by the following general formula (12). It can be obtained by (co)polymerizing (meth)acrylate monomers.

In general formula (3), R ¹ , R ² and R ³ represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.

In the general formula (12), R ¹⁸ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and R ¹⁹ represents an aliphatic group having 1 to 6 carbon atoms. A represents a urethane group represented by the following formula (A-1) or (A-2).

Preferred examples of the (meth)acrylamide monomer represented by general formula (3) include N,N-dimethylacrylamide and N,N-diethylacrylamide.

Moreover, the following structure is mentioned as a preferable example of the (meth)acrylate monomer represented by General formula (12).

Since the compatibility with the alkali-soluble resin (B) is easily improved, the total of the structural units represented by the general formula (1) or the general formula (11) is the entire structural unit constituting the liquid repellent material (A). It is preferably 15 mol% or more, more preferably 30 mol% or more. Further, in order to further improve liquid repellency, the amount is preferably 85 mol% or less, and more preferably 70 mol% or less.

In the first embodiment of the photosensitive resin composition of the present invention, the liquid repellent material (A) having at least an amide group or a urethane group preferably contains a compound having a urethane group from the viewpoint of improving alkali solubility. , it is more preferable to contain a compound having a structural unit represented by general formula (11). By improving the alkali solubility, the amount of residue in the openings during alkali development is reduced, so that the wettability of the functional ink applied to the openings can be further improved. As a result, the uniformity of the film thickness of the functional layer formed from the functional ink becomes easier to improve, the display defects of the display device become easier to reduce, and the durability becomes easier to improve.

The liquid repellent material (A) having at least an amide group or a urethane group preferably contains a structural unit represented by general formula (2) or a compound having a structure represented by general formula (13). By having the structural unit represented by the general formula (2) or the structure represented by the general formula (13), liquid repellency can be easily imparted to the surface of the cured film.

In the general formula (2), R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, R ⁵ represents an aliphatic group having 1 to 6 carbon atoms, and R ⁶ represents a paroxylic group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.

In general formula (13), X is selected from the following structural formulas (a) to (e), and all Xs may have the same structure, or multiple structures may exist randomly or in a block shape. . m is an integer from 1 to 100 representing the number of repeating units.

The compound having the structural unit represented by the general formula (2) or the structure represented by the general formula (13) is, for example, a (meth)acrylate monomer represented by the general formula (4) or a compound having the structure represented by the general formula (13). It can be obtained by (co)polymerizing monomers having the structure represented by:

In the general formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, R ⁵ represents an aliphatic group having 1 to 6 carbon atoms, and R ⁶ represents a paroxylic group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.

Preferred examples of the (meth)acrylate monomer having a perfluoroalkyl group represented by the general formula (4) include 2-(perfluorobutyl)ethyl(meth)acrylate, 2-(perfluorohexyl)ethyl(meth)acrylate, and 2-(perfluorohexyl)ethyl(meth)acrylate. ) acrylate, etc.

Preferred examples of the monomer having the structure represented by general formula (13) include monomers having the following structure.

In the first embodiment of the photosensitive resin composition of the present invention, the liquid repellent material (A) having at least an amide group or a urethane group is represented by general formula (13) from the viewpoint of further improving alkali solubility. It is preferable to contain a compound having a structure. By further improving the alkali solubility, the amount of residue in the openings during alkali development is reduced, so that the wettability of the functional ink applied to the openings can be further improved. As a result, the film thickness uniformity of the functional layer formed from the functional ink is improved, making it easier to reduce display defects and improve durability of the display device.

In the first aspect of the photosensitive resin composition of the present invention, the liquid repellent material (A) having at least an amide group or a urethane group contains a urethane group and a compound having a structure represented by general formula (13). By including such a compound, the alkali solubility of component (A) can be further improved. The first aspect of the photosensitive resin composition of the present invention more preferably contains a compound having a structural unit represented by general formula (11) and a structure represented by general formula (13).

A liquid repellent which is a compound having a urethane group and a structure represented by general formula (13), and which also includes a compound having a structural unit represented by general formula (11) and a structure represented by general formula (13). Commercially available materials include “Megafac (registered trademark)” RS-72-K, RS-72-A, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 ( (manufactured by DIC Corporation).

The liquid repellent material (A) having at least an amide group or a urethane group preferably further has an epoxy group. By having an epoxy group, it becomes easier to polycondense with the alkali-soluble resin (B) and further improve the durability as a light emitting element. It is more preferable that component (A) further has a structural unit represented by general formula (5). Component (A) having a structural unit represented by general formula (5) can be obtained by copolymerizing, for example, an epoxy group-containing (meth)acrylate monomer represented by general formula (6) as one of the copolymerization components. You can get it at

In the general formulas (5) and (6), R ⁷ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and R ⁸ represents a monovalent organic group having 2 to 16 carbon atoms having an epoxy group.

Preferred examples of the epoxy group-containing (meth)acrylate monomer represented by general formula (6) include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE), and 4-hydroxybutyl methacrylate glycidyl ether. , acrylate having an alicyclic epoxy group, and metharylate having an alicyclic epoxy group.

Further, the structural unit represented by the general formula (5) preferably accounts for 10 mol% or more, more preferably 20 mol% or more of the total structural units constituting the liquid repellent material (A). Within this range, when forming a cured film of the photosensitive resin composition, polycondensation will occur with the alkali-soluble resin (B) to form a cured film with high heat resistance. The heat resistance is improved and the durability of the display device is improved. Further, in order to obtain the effect of improving liquid repellency and compatibility with the alkali-soluble resin (B), the amount is preferably 50 mol% or less, and more preferably 40 mol% or less.

The liquid repellent material (A) having at least an amide group or a urethane group may be a copolymer obtained by copolymerizing a different functional group-substituted (meth)acrylic monomer. Furthermore, by copolymerizing different functional group-substituted (meth)acrylic monomers, it is possible to easily balance liquid repellency and solubility. For example, hydroxyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylamides, alkoxy group-containing (meth)acrylates, blocked isocyanate group-containing (meth)acrylates, phenoxy group-containing (meth)acrylates, alkyl (meth)acrylates. Examples include acrylates and vinyl group-containing compounds.

Examples of the hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate.

Examples of the hydroxyl group-containing (meth)acrylamides include N-hydroxymethylacrylamide.

Examples of the (meth)acrylates having an alkoxy group include 3-methacryloxypropylmethyldimethoxysilane.

Examples of blocked isocyanate group-containing (meth)acrylates include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karens MOI-BM: manufactured by Showa Denko K.K.; registered trademark). Can be mentioned.

Examples of the phenoxy group-containing (meth)acrylates include 2-phenoxybenzyl acrylate and 3-phenoxybenzyl acrylate.

Alkyl (meth)acrylates are unsubstituted, substituted with at least one of an amino group, a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring, or a heterocycle, or have an acid anhydride cleaved and added to a hydroxy group. Examples include diluent monomers that are unsubstituted or substituted alkyl (meth)acrylates having a linear, branched, and/or cyclic alkyl group having 1 to 12 carbon atoms, such as alkyl acrylates.

Examples of vinyl group-containing compounds include n-butyl vinyl ether.

The compound contained in the liquid repellent material (A) having at least an amide group or a urethane group is usually a (co)polymer. The (co)polymer as a compound contained in the liquid repellent (A) can be obtained by a known polymerization method. The (co)polymer may be obtained by, for example, ionic polymerization such as radical polymerization or anionic polymerization. Further, it may be a random copolymer, a block copolymer, a graft (co)polymer, or an alternating copolymer. Here, a radical (co)polymerization method will be taken as an example. For example, a predetermined amount of dimethyl (meth)acrylamide, a predetermined amount of a fluorine-containing (meth)acrylate monomer, and, if necessary, a predetermined amount of epoxy group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, hydroxyl group-containing (Meth)acrylamides, alkoxy group-containing (meth)acrylates, blocked isocyanate group-containing (meth)acrylates, phenoxy group-containing (meth)acrylates, alkyl (meth)acrylates, and vinyl group-containing compounds in an appropriate solvent. Component (A) can be obtained by random copolymerization in the presence of a radical polymerization initiator and, if necessary, a chain transfer agent. As the radical polymerization initiator, for example, tert-butylperoxy-2-ethylhexanoate can be used. As the chain transfer agent, for example, dodecyl mercaptan can be used. Further, as the solvent, for example, an inert solvent such as cyclohexanone can be used.

The weight average molecular weight of the liquid repellent material (A) having at least an amide group or a urethane group is preferably in the range of 1,500 to 50,000. By setting the molecular weight within this range, it can be more easily dissolved in the solvent used for the photosensitive resin composition. Further, by setting the molecular weight within this range, the antifoaming property of the photosensitive resin composition solution tends to be high.

The liquid repellent material (A) having at least an amide group or a urethane group has a content of 0.00 parts by weight per 100 parts by mass of the alkali-soluble resin (B), from the viewpoint that the resulting cured film is likely to exhibit sufficient liquid repellency. The amount is preferably 1 part by mass or more, and more preferably 0.3 parts by mass or more. Further, from the viewpoint of making it difficult to cause liquid repellency in the pixel and easily achieving high durability, the amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

The first aspect of the photosensitive resin composition of the present invention contains an alkali-soluble resin (B) (hereinafter sometimes referred to as component (B)). In the first embodiment of the photosensitive resin composition of the present invention, the alkali-soluble resin refers to a resin having a dissolution rate defined below of 50 nm/min or more. Specifically, a solution of a resin dissolved in γ-butyrolactone was applied onto a silicon wafer, and prebaked at 120°C for 4 minutes to form a prebaked film with a thickness of 10 μm ± 0.5 μm. Refers to a resin whose dissolution rate, determined from the decrease in film thickness when rinsed with pure water after being immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 1°C for 1 minute, is 50 nm/min or more.

In the first embodiment of the photosensitive resin composition of the present invention, the alkali-soluble resin (B) may have an alkali-soluble group in the structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility. preferable. The alkali-soluble group refers to a functional group that increases solubility in an alkaline solution by interacting or reacting with an alkali, and specifically includes an acidic group. Preferred alkali-soluble groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups.

The alkali-soluble resin (B) in the first aspect of the present invention contains at least one alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. . These alkali-soluble resins may be used alone or in combination. Since these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgassing at high temperatures of 200° C. or higher after heat treatment is reduced, and the durability of the display device can be increased.

Preferred embodiments of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof used as the alkali-soluble resin (B) can be found in the second section of the photosensitive resin composition of the present invention described below. This is the same as the explanation regarding the alkali-soluble resin (BI) in the embodiment.

The first aspect of the photosensitive resin composition of the present invention further includes at least one resin (C) selected from the group consisting of phenol resins and polyhydroxystyrene resins (hereinafter sometimes referred to as component (C)). ) is preferably contained. These resins have a function as a compatibilizer, and by mixing them, the compatibility of components (A) and (B) is improved, and the solubility of each component in the developer is stabilized. This contributes to the improvement of the straightness of the pattern. As a result, it is expected that display defects in the display device will be reduced. In addition, when using a positive type photosensitive agent (E), which will be described later, containing component (C) can reduce the amount of film loss during the development process. It has the effect of making it easier to stay on the surface, and can improve the process margin for obtaining good liquid repellency.

In the first embodiment of the photosensitive resin composition of the present invention, at least one resin selected from the group consisting of the phenol resin and polyhydroxystyrene resin is added to 100 parts by mass of the alkali-soluble resin (B). The total amount of (C) is preferably 10 to 100 parts by mass. From the viewpoint of improving the compatibility of components (A) and (B), improving the straightness of the pattern, and easily reducing display defects in display devices, the total amount of components (C) should be 10 parts by mass or more. The amount is preferably 30 parts by mass or more, and more preferably 30 parts by mass or more. Moreover, from the viewpoint of making it difficult to reduce the durability of the cured film of the photosensitive resin composition, the amount is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.

Preferred embodiments of the at least one resin (C) selected from the group consisting of phenolic resins and polyhydroxystyrene resins include phenolic resins and polyhydroxystyrene resins in the second embodiment of the photosensitive resin composition of the present invention described below. The explanation for at least one type of resin (C-I) is as follows.

It is preferable that the first aspect of the photosensitive resin composition of the present invention further contains a thermal crosslinking agent (D). By containing the thermal crosslinking agent (D), the durability of the display device can be more easily improved. Preferred embodiments of the thermal crosslinking agent (D) are as described below for the thermal crosslinking agent (DI) in the second embodiment of the photosensitive resin composition of the present invention.

The first aspect of the photosensitive resin composition of the present invention contains a photosensitizer (E). The photosensitizer (E) may be a negative type that is cured by light or a positive type that is solubilized by light. As the photosensitizer (E), (e-1) a polymerizable unsaturated compound and a photopolymerization initiator, or (e-2) a quinonediazide compound, etc. can be preferably contained. In the first embodiment of the photosensitive resin composition of the present invention, a positive type is preferable from the viewpoint of forming a step-shaped partition wall to be processed later in one photolithography process by halftone processing. Preferred embodiments of the photosensitizer (E) are as explained below for the photosensitizer (EI) in the second embodiment of the photosensitive resin composition of the present invention.

It is preferable that the first embodiment of the photosensitive resin composition of the present invention further contains a colorant (F). Specific examples of the colorant (F) include known organic pigments, inorganic pigments, and dyes commonly used in the field of electronic information materials. The colorant (F) is preferably an organic pigment and/or an inorganic pigment. Preferred embodiments of the colorant (F) are as described below for the colorant (F-I) in the second embodiment of the photosensitive resin composition of the present invention.

The first aspect of the photosensitive resin composition of the present invention preferably contains an organic solvent (G). Examples of the organic solvent (G) include compounds such as ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols. Preferred embodiments of the organic solvent (G) are as described below for the organic solvent (GI) in the second embodiment of the photosensitive resin composition of the present invention.

The first aspect of the photosensitive resin composition of the present invention can contain an adhesion improver. Preferred embodiments of the adhesion improver are as described below regarding the adhesion agent in the second embodiment of the photosensitive resin composition of the present invention.

Next, a method for producing the photosensitive resin composition of the present invention will be explained. The first embodiment of the photosensitive resin composition of the present invention can be obtained, for example, by dissolving the components (A) to colorant (F) in an organic solvent (G). Examples of the dissolution method include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually 20°C to 80°C. Further, the order of dissolving each component is not particularly limited, and for example, there is a method of dissolving compounds in order starting from the one with the lowest solubility.

The obtained photosensitive resin composition is preferably filtered using a filter to remove dust and particles. Preferred embodiments of the filtration filter are as described below regarding the filtration filter in the second embodiment of the photosensitive resin composition of the present invention.

The first embodiment of the cured film of the present invention consists of a cured product of the first embodiment of the photosensitive resin composition of the present invention.

The description of the method for producing the first embodiment of the cured film of the present invention corresponds to the method for producing the cured film of the second embodiment of the photosensitive resin composition of the present invention, which will be described later.

The first embodiment of the cured film of the present invention can be used for electronic components such as organic EL display devices, semiconductor devices, and multilayer wiring boards. Specifically, partition walls of organic EL elements, planarization layers of substrates with drive circuits of display devices using organic EL elements, interlayer insulating films between rewirings of semiconductor devices or semiconductor components, passivation films of semiconductors, and semiconductor elements. Suitable for use in applications such as protective films for high-density packaging, interlayer insulation films for multilayer wiring for high-density packaging, wiring protection insulation layers for circuit boards, on-chip microlenses for solid-state imaging devices, and flattening layers for various displays and solid-state imaging devices. . Examples of electronic devices having a surface protective film, interlayer insulating film, etc. in which the first embodiment of the cured film of the present invention is disposed include a magnetoresistive memory (hereinafter referred to as MRAM) with low heat resistance. That is, the first embodiment of the cured film of the present invention is suitable for use as a surface protective film for MRAM. Further, a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, specifically, a display such as an LCD, an ECD, an ELD, an organic EL, etc. It can be used for partition walls and insulating layers of devices. More preferably, it can be used as a partition wall of a display device in which a functional layer is formed by applying functional ink in a region (pixel) surrounded by a grid-like partition wall formed on a substrate using an inkjet. The first aspect of the cured film of the present invention has good liquid repellency and prevents ink applied by an inkjet method from penetrating into adjacent pixels, thereby reducing the occurrence of display defects. Further, in the first aspect of the cured film of the present invention, since the amount of outgassing is small at high temperatures, the functional layer includes at least one material selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material. It can be suitably used in organic EL display devices including the above.

The first aspect of the cured film of the present invention is based on JIS-R3258, and the contact angle on the surface of the cured film when propylene glycol monomethyl ether acetate is dropped by the sessile drop method is 30° or more. The angle is preferably 40° or more, and more preferably 40° or more. The contact angle on the surface of the cured film increases, for example, by increasing the content of the liquid repellent material (A) having at least an amide group or urethane group, and decreases by decreasing the content of the liquid repellent material (A). Therefore, for example, the above range can be achieved by adjusting the content of the liquid repellent material (A) having at least an amide group or a urethane group.

A first embodiment of the display device of the present invention is a display device having a grid-like partition wall formed on a substrate, and the partition wall includes the first embodiment of the cured film of the present invention. By including the first aspect of the cured film of the present invention, it is possible to reduce the occurrence of display defects in a display device. Furthermore, the amount of outgassing at high temperatures of 200° C. or higher after heat treatment is reduced, and the durability of the display device can be improved. Furthermore, since the first aspect of the cured film of the present invention has good liquid repellency, ink applied by an inkjet method within pixels surrounded by lattice-like partition walls does not penetrate into adjacent pixels. By preventing this, the occurrence of display defects is reduced.

In a first aspect of the display device of the present invention, the lattice-shaped partition formed on the substrate is a first partition whose cross section cut perpendicularly to the longitudinal direction of the partition and the surface of the substrate is trapezoidal. and a second partition having a trapezoidal cross section above the first partition, and in the cross section, the width of the upper surface of the first partition is A, and the second partition is When the width of the bottom surface of the portion is defined as B, it is preferable that the relationship A>B is satisfied. FIG. 1 shows an example of a schematic cross-sectional view of a lattice-shaped partition formed on a substrate, cut perpendicular to the longitudinal direction of the partition and the surface of the substrate. The partition wall is formed on the substrate 8 having the first electrode 2 . In the example of FIG. 1, the partition wall has a stepped shape having a second partition wall portion 10 having a trapezoidal cross section above the first partition wall portion 9, and satisfies the relationship A>B.

Generally, when forming a functional layer by applying functional ink using an inkjet in an area (pixel) surrounded by lattice-like partition walls formed on a substrate, after applying the functional ink, A functional layer is formed by drying the solvent contained in the layer. Since the drying of the ink droplets starts near the partition walls, the viscosity of the ink near the partition walls tends to increase as the drying progresses. For this reason, it is known that the thickness of the functional layer is thicker at the ends than at the center. In the case of an organic EL display device, this causes a problem in that the brightness differs between the center and the outer periphery of the pixel.

When the functional ink is applied by an inkjet to the area surrounded by the grid-like partition walls having the stepped shape in the first aspect of the display device of the present invention, the end portion of the thick functional layer is applied to the first partition wall portion. It can be formed on the top surface. That is, it is possible to create a shape in which the end of the functional layer is located on the side surface of the second partition wall in a plane cut in a direction perpendicular to the substrate. With such a structure, the end portion of the thick functional layer can be prevented from emitting light by the first partition, and only the area where the thickness of the functional layer is uniform can be made to emit light. As a result, it is possible to eliminate the problem of brightness differences between the center and edges of a pixel. In an example of a schematic cross-sectional view of a partition wall in FIG. 1, a functional layer 11 and an end 12 of the functional layer are shown.

In the first embodiment of the display device of the present invention, the thickness of the partition wall is preferably 0.5 to 5.0 μm. If the thickness is 0.5 μm or more, the functional ink can be easily retained within the pixel. From the viewpoint of making it easier to process the photosensitive resin composition by photolithography, the thickness of the partition walls is preferably 5.0 μm or less. Further, it is preferable that the film thickness of the first partition wall portion is 0.1 to 1.0 μm. If the film thickness of the first partition wall is 0.1 μm or more, the insulation required of the partition wall can be maintained. When the thickness of the first partition wall portion is 1.0 μm or less, a thick functional layer end portion can be formed above the first partition wall portion. In the first aspect of the display device of the present invention, the thickness of the partition wall is 0.5 to 5.0 μm, and the thickness of the first partition wall is 0.1 to 1.0 μm. , more preferred.

In the first aspect of the display device of the present invention, it is preferable that the first partition wall portion and the second partition wall portion are formed from a cured film of the same material. In the present invention, "the same material" refers to products made from the same photosensitive resin composition. According to the first embodiment of the photosensitive resin composition of the present invention, a stepped shape can be easily formed by one photolithography process using a half-exposure process.

In the first aspect of the display device of the present invention, it is preferable that a functional layer is formed in a region surrounded by partition walls of the display device. For example, by forming a colored layer that colors transmitted light and arranging a plurality of colored layers having different colors for each pixel, it can be used as a color filter. Alternatively, by forming an organic EL light emitting layer containing at least one selected from organic EL light emitting materials, hole injection materials, and hole transport materials, it can be used as an organic EL display device.

In a first aspect of the display device of the present invention, an end of the functional layer is located on a side surface of the second partition in a cross section cut perpendicular to the longitudinal direction of the partition and the surface of the substrate. It is preferable. If the end of the functional layer is located on the side surface of the second partition, the end of the thick functional layer is prevented from emitting light by the first partition, and the functional layer has an area with a uniform thickness. can only emit light. As a result, it is possible to eliminate the problem of brightness differences between the center and edges of a pixel.

In a first aspect of the organic EL display device of the present invention, the functional layer of the display device includes at least one type selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material. An organic EL light emitting layer can be formed by containing at least one type selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transporting material in the functional layer.

A first aspect of the organic EL display device of the present invention has a driving circuit, a planarization layer, a first electrode, a partition wall, an organic EL light emitting layer, and a second electrode on a substrate, and the partition wall is a hardened layer according to the present invention. The first aspect of the membrane consists of: Taking an active matrix display device as an example, it has a TFT on a substrate such as glass or a resin film, and wiring located on the side of the TFT and connected to the TFT, and covering unevenness on top of the TFT. In this manner, a flattening layer is provided, and a display element is further provided on the flattening layer. The display element and the wiring are connected through contact holes formed in the planarization layer.

By using the first embodiment of the cured film of the present invention for the partition wall, it has liquid repellency and prevents the ejected liquid used in the inkjet method from penetrating into adjacent pixels, thereby reducing the occurrence of display defects. It is possible to obtain an organic EL display device with a small amount of organic EL display device and excellent durability.

Next, a first aspect of the method of manufacturing a partition-walled substrate of the present invention and a first aspect of the method of manufacturing a display device of the present invention will be described.

The first embodiment of the method for manufacturing a substrate with partition walls of the present invention includes the following steps (1) to (4) in this order.
(1) Step of applying the first embodiment of the photosensitive resin composition of the present invention on a substrate having a first electrode to form a photosensitive resin film (2) Step of exposing the photosensitive resin film (3) ) A step of developing the exposed photosensitive resin film; (4) A step of forming partition walls by heat-treating the developed photosensitive resin film.

First, the process of (1) applying a photosensitive resin composition to a substrate having a first electrode to form a photosensitive resin film will be described.

Examples of the method for applying the photosensitive resin composition to the substrate having the first electrode include a spin coating method, a slit coating method, a dip coating method, a spray coating method, and a printing method. Prior to coating, the substrate to which the photosensitive resin composition is applied may be pretreated with the adhesion improver described above. For example, a solution in which 0.5 to 20% by mass of the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. is used. Examples include methods of treating the surface of the base material. Examples of methods for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

Next, for example, the applied photosensitive resin film is subjected to a vacuum drying treatment as necessary, and then heat treated at a temperature of 50°C to 180°C for 1 minute to several hours using a hot plate, oven, infrared rays, etc. By applying this, a dry photosensitive resin film can be obtained.

Next, the step (2) of exposing the photosensitive resin film will be explained.

Actinic radiation is irradiated onto the photosensitive resin film through a photomask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays, but in the present invention, it is preferable to use I-lines (365 nm), H-lines (405 nm), and G-lines (436 nm) from a mercury lamp. . After irradiating with actinic radiation, a post-exposure bake may be performed. By performing post-exposure baking, effects such as improved resolution after development or increased allowable range of development conditions can be expected. For post-exposure baking, an oven, hot plate, infrared rays, flash annealing device, laser annealing device, or the like can be used. The post-exposure bake temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure bake time is preferably 10 seconds to several hours. When the post-exposure bake time is within the above range, the reaction proceeds favorably and the development time may be shortened.

In the present invention, by "half exposure", the substrate has a stepped shape having a first partition wall section having a trapezoidal cross section and a second partition wall section having a trapezoidal cross section above the first partition wall section. When the width of the top surface of the first partition wall section is A and the width of the bottom surface of the second partition wall section is B, it is easy to form a step shape that satisfies the relationship A>B. can do.

"Half exposure" refers to a process in which a certain amount of the underlayer of the photosensitive resin film remains in the exposed area when development is completed. In other words, it refers to a process in which exposure is performed so that the first partition part of the photosensitive resin film is not exposed to light.

Next, the step (3) of developing the exposed photosensitive resin film will be explained.

In the development step of developing the exposed photosensitive resin film, the exposed photosensitive resin film is developed using a developer to remove areas other than the exposed areas. As a developer, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl Aqueous solutions of alkaline compounds such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine are preferred. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination. good. As the developing method, methods such as spray, paddle, immersion, and ultrasonic waves are possible.

Next, the pattern formed by development is preferably rinsed with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may be added to distilled water for rinsing.

Next, the step (4) of forming partition walls by heat-treating the developed photosensitive resin film will be described.

A cured film is obtained by heat-treating the developed photosensitive resin film. In the present invention, a cured film of a photosensitive resin composition can be suitably used as a partition wall of an organic EL display device. Since residual solvent and components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. Moreover, when containing a thermal crosslinking agent (D), a thermal crosslinking reaction can be advanced by heat treatment, and heat resistance and chemical resistance can be improved. This heat treatment is carried out by selecting a temperature and increasing the temperature stepwise, or by selecting a certain temperature range and increasing the temperature continuously for 5 minutes to 5 hours. An example is a method of heat treatment at 150° C. and 250° C. for 30 minutes each. Alternatively, a method may be used in which the temperature is linearly raised from room temperature to 300° C. over 2 hours. The heat treatment conditions in the present invention are preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher. The heat treatment conditions are preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower.

The first embodiment of the method for manufacturing a display device of the present invention includes the following steps (5) to (6) in this order.
(5) In a partition-equipped substrate having partition walls containing the cured product of the first embodiment of the photosensitive resin composition of the present invention, a functional ink is applied by an inkjet to the area surrounded by the partition walls to form a functional layer. Step (6) of forming a second electrode on the functional layer.

First, (5) in a partition-equipped substrate having partition walls containing the cured product of the first embodiment of the photosensitive resin composition of the present invention, a functional ink is applied by an inkjet to an area surrounded by the partition walls to provide a functional The process of forming layers will be explained.

A functional layer is formed by applying functional ink using an inkjet method within regions (pixels) surrounded by lattice-like partition walls formed on a substrate. For example, in the case of an organic EL display device, a composition containing at least one selected from the group consisting of an organic EL luminescent material, a hole injection material, and a hole transport material is dropped as a functional ink into pixels and dried. By this, an organic EL light emitting layer can be formed. For drying, it is preferable to use a hot plate or oven and heat at 150° C. to 250° C. for 0.5 minutes to 120 minutes.

Next, the step (6) of forming a second electrode on the functional layer will be explained.

A second electrode is formed to cover the entire partition wall and functional layer. Examples of methods for forming the second electrode include sputtering, vapor deposition, and the like. Note that it is preferable to form the second electrode with a uniform layer thickness without any disconnection.

The first embodiment of the method for manufacturing a display device of the present invention preferably includes the following steps (1) to (6) in this order.
(1) Step of applying the first embodiment of the photosensitive resin composition of the present invention on a substrate having a first electrode to form a photosensitive resin film (2) Step of exposing the photosensitive resin film to light (3) Step of developing the exposed photosensitive resin film (4) Step of forming partition walls by heating the developed photosensitive resin film (5) Applying functional ink within the area surrounded by the partition walls using an inkjet. (6) forming a second electrode on the functional layer;

A second aspect of the photosensitive resin composition of the present invention is a compound (AI) having at least structural units represented by general formula (1) and general formula (2) (hereinafter referred to as compound (AI)). ) and an alkali-soluble resin (BI) selected from polyimide, polybenzoxazole, polyamideimide, precursors of any of these, and copolymers thereof. In this specification, the photosensitive resin composition in the second embodiment of the photosensitive resin composition of the present invention may be referred to as photosensitive resin composition (I).

In general formula (1), R ¹ , R ² and R ³ represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.

In the general formula (2), R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, R ⁵ represents an aliphatic group having 1 to 6 carbon atoms, and R ⁶ represents a paroxylic group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.

Compound (A-I) is a compound in which at least a (meth)acrylamide monomer represented by general formula (3) and a (meth)acrylate monomer having a perfluoro group represented by general formula (4) are copolymerized. It is a liquid repellent material that is compatible with the photosensitive resin composition (I) and is added to impart liquid repellency to the surface of the cured film.

In general formula (3), R ¹ , R ² and R ³ represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.

In the general formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, R ⁵ represents an aliphatic group having 1 to 6 carbon atoms, and R ⁶ represents a paroxylic group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.

Preferred examples of the (meth)acrylamide monomer represented by general formula (3) include N,N-dimethylacrylamide and N,N-diethylacrylamide. Further, as preferred examples of the (meth)acrylate monomer having a perfluoro group represented by the general formula (4), 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl ( meth)acrylate, etc.

Compound (AI) has a structural unit represented by general formula (1) obtained by copolymerizing a (meth)acrylamide monomer represented by general formula (3). The structural unit represented by the general formula (1) has the effect of improving compatibility with the alkali-soluble resin (B) described later, reducing defects such as repellency, and improving the uniformity of the thickness of the cured film. As a result, display defects in the organic EL display device are reduced. From the viewpoint of reducing display defects in organic EL display devices, the structural unit represented by general formula (1) preferably accounts for 35 mol% or more of the total structural units constituting the compound (AI), and more preferably 40 mol%. % or more and the largest molar ratio among the plurality of structural units constituting compound (AI). Further, in order to impart liquid repellency, the content is preferably 85 mol% or less, more preferably 70 mol% or less.

Compound (A-I) is a general compound for the purpose of polycondensing with alkali-soluble resin (B) to further improve durability as a light-emitting element when forming a cured film of photosensitive resin composition (I). It is preferable to have a structural unit represented by formula (5), and more preferably a copolymer copolymerized with an epoxy group-containing (meth)acrylate monomer represented by general formula (6).

In the general formulas (5) and (6), R ⁷ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and R ⁸ represents a monovalent organic group having 2 to 16 carbon atoms having an epoxy group.

Preferred examples of the epoxy group-containing (meth)acrylate monomer represented by general formula (6) include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE), and acrylates having an alicyclic epoxy group. Examples include monomers.

Furthermore, if the structural unit represented by the general formula (5) has an equimolar or higher molar ratio with the structural unit represented by the general formula (2), the cured film of the photosensitive resin composition (I) can be formed. During formation, the photosensitive resin composition (I) undergoes polycondensation with the alkali-soluble resin (B) to form a cured film with high heat resistance, increasing the heat resistance of the cured film of the photosensitive resin composition (I) and improving the durability of the organic EL display device. It is more preferable because it improves.

Compound (AI) may be a copolymer obtained by copolymerizing a different functional group-substituted (meth)acrylic monomer for the purpose of balancing liquid repellency and solubility. For example, hydroxyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylamides, alkoxy group-containing (meth)acrylates, blocked isocyanate group-containing (meth)acrylates, phenoxy group-containing (meth)acrylates, alkyl (meth)acrylates. Examples include acrylates and vinyl group-containing compounds.

Examples of the hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate.
Examples of the hydroxyl group-containing (meth)acrylamides include N-hydroxymethylacrylamide.
Examples of the (meth)acrylates having an alkoxy group include 3-methacryloxypropylmethyldimethoxysilane.
Examples of blocked isocyanate group-containing (meth)acrylates include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karens MOI-BM: manufactured by Showa Denko K.K.; registered trademark). Can be mentioned.

Examples of the phenoxy group-containing (meth)acrylates include 2-phenoxybenzyl acrylate and 3-phenoxybenzyl acrylate.

Alkyl (meth)acrylates are unsubstituted, substituted with at least one of an amino group, a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring, or a heterocycle, or have an acid anhydride cleaved and added to a hydroxy group. Examples include diluent monomers that are unsubstituted or substituted alkyl (meth)acrylates having a linear, branched, and/or cyclic alkyl group having 1 to 12 carbon atoms, such as alkyl acrylates.

Examples of vinyl group-containing compounds include n-butyl vinyl ether.

The copolymer of compound (AI) may be obtained by ionic polymerization such as radical polymerization or anionic polymerization, and can be obtained by a known polymerization method. Further, it may be a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer. Here, a radical polymerization method will be taken as an example. For example, a predetermined amount of dimethyl (meth)acrylamide, a predetermined amount of a fluorine-containing (meth)acrylate monomer, and, if necessary, a predetermined amount of epoxy group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, hydroxyl group-containing (Meth)acrylamides, alkoxy group-containing (meth)acrylates, blocked isocyanate group-containing (meth)acrylates, phenoxy group-containing (meth)acrylates, alkyl (meth)acrylates, and vinyl group-containing compounds in an appropriate solvent. Compound (AI) can be obtained by random copolymerization in the presence of a radical polymerization initiator and, if necessary, a chain transfer agent. As the radical polymerization initiator, for example, tert-butylperoxy-2-ethylhexanoate can be used, and as the chain transfer agent, for example, dodecyl mercaptan can be used. Further, as the solvent, for example, an inert solvent such as cyclohexanone can be used.

The weight average molecular weight of the compound (A-I) is preferably in the range of 1,500 to 50,000, and if the molecular weight is within this range, it can be easily dissolved in the solvent used in the photosensitive resin composition (I). This is preferable because it allows the photosensitive resin composition solution to have high antifoaming properties.

In the present invention, the compound (A-I) is based on 100 parts by mass of an alkali-soluble resin (B) selected from polyimide, polybenzoxazole, polyamideimide, a precursor thereof, and a copolymer thereof, as described below. From the viewpoint that the obtained cured film sufficiently exhibits liquid repellency, the amount is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more. Further, from the viewpoint of not causing liquid repellency within the pixel and obtaining high durability, the amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. The appropriate amount of compound (A-I) to be added can be determined using the contact angle when propylene glycol monomethyl ether acetate is dropped onto the cured film surface of photosensitive resin composition (I). It is preferable that the contact angle is 40° or more when measured by the sessile drop method in accordance with JIS-R3258.

The photosensitive resin composition (I) is an alkali-soluble resin (BI) selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof (hereinafter referred to as (BI)). (sometimes referred to as components). Further, it may contain two or more types selected from polyimide, polybenzoxazole, polyamideimide, and precursors of any of these, or may contain a copolymer having repeating units of two or more of these types.

The alkali solubility in the second embodiment of the photosensitive resin composition of the present invention means that a solution of the resin dissolved in γ-butyrolactone is applied onto a silicon wafer, prebaked at 120°C for 4 minutes, and the film thickness is 10 μm±0. Determined from the decrease in film thickness when a .5 μm prebaked film is formed, the prebaked film is immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23±1°C for 1 minute, and then rinsed with pure water. It means that the dissolution rate is 50 nm/min or more.

Polyimide can be obtained, for example, by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic diester dichloride, etc. with diamine, diisocyanate compound, trimethylsilylated diamine, etc. Polyimide has tetracarboxylic acid residues and diamine residues. Moreover, polyimide can be obtained by, for example, dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting a tetracarboxylic dianhydride and a diamine, by heat treatment. During this heat treatment, a solvent that is azeotropic with water, such as m-xylene, may be added. Alternatively, it can also be obtained by adding a dehydration condensing agent such as a carboxylic acid anhydride or dicyclohexylcarbodiimide, or a base such as triethylamine as a ring-closing catalyst, and dehydrating and ring-closing it by chemical heat treatment. Alternatively, it can also be obtained by adding a weakly acidic carboxylic acid compound and performing dehydration ring closure by heat treatment at a low temperature of 100° C. or lower.

Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol compound with a dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, or the like. Polybenzoxazole has dicarboxylic acid residues and bisaminophenol residues. Further, polybenzoxazole can be obtained, for example, by dehydrating and ring-closing polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound and a dicarboxylic acid, by heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc., and dehydrating and ring-closing it by chemical treatment.

Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide, and the like. For example, polyamic acid can be obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic diester dichloride, or the like with a diamine, a diisocyanate compound, or a trimethylsilylated diamine. Polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained by the above method by heating or chemical treatment with an acid or a base.

Examples of the polybenzoxazole precursor include polyhydroxyamide. For example, polyhydroxyamide can be obtained by reacting bisaminophenol with dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, or the like. Polybenzoxazole can be obtained, for example, by dehydrating and ring-closing polyhydroxyamide obtained by the above method by heating or chemical treatment with phosphoric anhydride, a base, a carbodiimide compound, or the like.

The polyamide-imide precursor can be obtained, for example, by reacting a tricarboxylic acid, a corresponding tricarboxylic anhydride, a tricarboxylic anhydride halide, or the like with a diamine or a diisocyanate. Polyamideimide can be obtained, for example, by dehydrating and ring-closing the precursor obtained by the above method by heating or by chemical treatment with an acid or a base.

The copolymer of polyimide, polybenzoxazole, and polyamideimide may be one of block copolymerization, random copolymerization, alternating copolymerization, graft copolymerization, or a combination thereof. For example, a block copolymer can be obtained by reacting polyhydroxyamide with a tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride, or the like. Furthermore, dehydration and ring closure can also be carried out by heating or chemical treatment with acids or bases.

The component (BI) preferably has a structural unit represented by any of the general formulas (7) to (10), and more preferably has a structural unit represented by (10). Two or more types of resins having these structural units may be contained, or two or more types of structural units may be copolymerized. The resin of component (BI) preferably contains 3 to 1000 structural units represented by any of the general formulas (7) to (10) in its molecule, and more preferably 20 to 200.

In general formulas (7) to (10), R ⁹ and R ¹² are tetravalent organic groups, R ¹⁰ , R ¹¹ and R ¹⁴ are divalent organic groups, R ¹³ is a trivalent organic group, and R ¹⁵ is a trivalent organic group. R 16 represents a divalent to tetravalent organic group and R ¹⁶ represents a divalent to divalent organic group. R ¹⁷ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. p represents an integer of 0 to 2, and q represents an integer of 0 to 10. n represents an integer from 0 to 2.

All of R ⁹ to R ¹⁶ preferably have an aromatic ring and/or an aliphatic ring.

In general formulas (7) to (10), R ⁹ is a tetracarboxylic acid derivative residue, R ¹¹ is a dicarboxylic acid derivative residue, R ¹³ is a tricarboxylic acid derivative residue, and R ¹⁵ is di-, tri- or tetra- Represents a carboxylic acid derivative residue. As the acid component constituting R ⁹ , R ¹¹ , R ¹³ , R ¹⁵ (COOR ¹⁷ ) _n (OH) _p , examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, and bis(carboxyphenyl)hexane. Examples of tricarboxylic acids include fluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, trimellitic acid, trimesic acid, diphenyl ethertricarboxylic acid, biphenyltricarboxylic acid, etc. Examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 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)ethane, carboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalene Aromatic tetracarboxylic acids such as tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, , butanetetracarboxylic acid, aliphatic tetracarboxylic acids such as 1,2,3,4-cyclopentanetetracarboxylic acid, and the like. Among these, in general formula (10), one or two carboxyl groups of each of tricarboxylic acid and tetracarboxylic acid correspond to COOR ¹⁵ groups. These acid components can be used as they are, or as acid anhydrides, active esters, and the like. Moreover, you may use these two or more types of acid components in combination.

In general formulas (7) to (10), R ¹⁰ , R ¹² , R ¹⁴ and R ¹⁶ represent diamine derivative residues. Examples of the diamine component constituting R ¹⁰ , R ¹² , R ¹⁴ , R ¹⁶ (OH)q include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) ) sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4- Hydroxyl group-containing diamines such as hydroxy)biphenyl and bis(3-amino-4-hydroxyphenyl)fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether, and thiol groups such as dimercaptophenylene diamine. Containing diamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diamino Diphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5- Naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl }Ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl,3,3'-diethyl-4,4'-diaminobiphenyl,2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3 Aromatic diamines such as ',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and their aromatic rings. Examples include compounds in which a portion of hydrogen atoms are replaced with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc., and alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine. These diamines can be used as they are or as corresponding diisocyanate compounds or trimethylsilylated diamines. Moreover, you may use these two or more types of diamine components in combination. In applications where heat resistance is required, it is preferable to use aromatic diamine in an amount of 50 mol% or more of the total diamine.

R ⁹ to R ¹⁶ in general formulas (7) to (10) can contain a phenolic hydroxyl group, a sulfonic acid group, a thiol group, etc. in their skeletons. By using a resin having an appropriate amount of phenolic hydroxyl group, sulfonic acid group, or thiol group, a positive photosensitive resin composition having appropriate alkali solubility can be obtained.

Further, it is preferable that the structural unit of the component (BI) contains a fluorine atom. Fluorine atoms impart water repellency to the surface of the film during alkaline development, making it possible to suppress seepage from the surface. The fluorine atom content in component (BI) is preferably 10% by mass or more in order to sufficiently prevent penetration of the interface, and is preferably 20% by mass or less in view of solubility in an aqueous alkaline solution.

In addition, in order to improve the storage stability of the resin composition, the main chain end of the resin of the component (B-I) is added with a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to seal with an end capping agent. The introduction ratio of the monoamine used as the terminal capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 60 mol% or less, particularly preferably 50 mol% or more, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as the terminal capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, based on the diamine component. or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different terminal groups may be introduced by reacting a plurality of terminal capping agents.

In the resin having a structural unit represented by any of the general formulas (7) to (9), the number of repeating structural units is preferably 3 or more and 200 or less. Further, in the resin having the structural unit represented by the general formula (10), the number of repeats of the structural unit is preferably 10 or more and 1000 or less. Within this range, a thick film can be easily formed.

Component (B-I) may consist only of structural units represented by any of the general formulas (7) to (10), or may be a copolymer or mixture with other structural units. There may be. In this case, it is preferable that the structural unit represented by any one of the general formulas (7) to (10) be contained in an amount of 10% by mass or more, more preferably 30% by mass or more based on the entire resin. The type and amount of structural units used for copolymerization or mixing can be selected within a range that does not impair the mechanical properties of the thin film obtained by the final heat treatment.

The photosensitive resin composition (I) further contains at least one resin (C-I) (hereinafter sometimes referred to as the (C-I) component) selected from a phenol resin and a polyhydroxystyrene resin. It is preferable to do so. These resins have a function as a compatibilizer, and by mixing them, the compatibility of the compound (AI) and (BI) component is further improved, and the solubility of each component in the developer is improved. This contributes to stabilization and improves the straightness of the pattern. As a result, it is expected that display defects in organic EL display devices will be reduced. In addition, when the photosensitive agent (E-I) to be used afterwards is a positive type, containing the (C-I) component can reduce the amount of film loss in the development process, so the compound (A-I) can be used as a positive type. It has the effect of staying on the film surface after development, and can improve the process margin for obtaining good liquid repellency.

Phenol resins include novolac phenol resins and resol phenol resins, and are obtained by polycondensing various phenols alone or in mixtures of a plurality of them using aldehydes such as formalin by a known method.

Examples of the phenols constituting the novolac phenol resin and resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethyl Phenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3- Dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropyl Examples include phenol, α-naphthol, β-naphthol, and the like, and these can be used alone or as a mixture of two or more. In addition to formalin, examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, and these can be used alone or as a mixture of a plurality of them.

As the polyhydroxystyrene resin, it is also possible to use a homopolymer of vinylphenol or a copolymer with styrene.
The preferable weight average molecular weight of the phenol resin and polyhydroxystyrene resin is 2,000 to 20,000, preferably 3,000 to 10,000 in terms of polystyrene measured by GPC (gel permeation chromatography). Within this range, a resin composition with high concentration and low viscosity can be obtained.

The total content of phenol resin and polyhydroxystyrene resin in photosensitive resin composition (I) is the amount of compound (AI) and (BI) component based on 100 parts by mass of component (BI). From the viewpoint of improving compatibility, improving the straightness of the pattern, and reducing display defects in organic EL display devices, the amount is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. Moreover, for the purpose of not reducing the durability of the cured film of the photosensitive resin composition, the amount is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less.

In order to easily obtain a cured film, the photosensitive resin composition (I) preferably further contains a thermal crosslinking agent (DI).
A thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups such as a methylol group, an alkoxymethyl group, an epoxy group, or an oxetanyl group in its molecule. The thermal crosslinking agent (DI) can crosslink component (BI) or other additive components, thereby increasing the durability of the cured film.

Preferred examples of compounds having at least two alkoxymethyl groups or methylol groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML- OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM- PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM- BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade names, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKALAC ( (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.), and each It can be obtained from each of the above companies.

Examples of compounds having epoxy groups or oxetanyl groups include "Epicote" (registered trademark) 807, "Epicote" 828, "Epicote" 1002, "Epicote" 1750, and "Epicote" having two epoxy groups in one molecule. 1007, YX8100-BH30, E1256, E4250, E4275 (all product names, manufactured by Japan Epoxy Co., Ltd.), "Epicron" (registered trademark) EXA-4880, "Epicron" EXA-4822, "Epicron" EXA-9583, HP4032 (The above product names are manufactured by Dainippon Ink and Chemicals Co., Ltd.), "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, "Epolite" 400E, "Epolite" 70P, "Epolite" 200P, “Epolite” 400P, “Epolite” 1500NP, “Epolite” 80MF, “Epolite” 4000, “Epolite” 3002 (all product names, manufactured by Kyoeisha Chemical Co., Ltd.), “Denacol” (registered trademark) EX-212L, “Denacol” "EX-214L," Denacol" EX-216L, "Denacol" Co., Ltd.), "Celoxide" (registered trademark) 2021P (product name, manufactured by Daicel Co., Ltd.), "Recaresin" (registered trademark) DME-100, "Recaresin" BEO-60E (product names, New Japan Chemical) Co., Ltd.), and can be obtained from each company.

In addition, as those having three or more epoxy groups, VG3101L (trade name, manufactured by Printec Co., Ltd.), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (trade name, Nissan Chemical Co., Ltd.) Kogyo Co., Ltd.), “Epiclon” N660, “Epiclon” N695, HP7200 (trade names, manufactured by Dainippon Ink & Chemicals Co., Ltd.), “Denacol” EX-321L (trade name, Nagase ChemteX Co., Ltd.) ), NC6000, EPPN502H, NC3000 (all product names, manufactured by Nippon Kayaku Co., Ltd.), "Epotote" (registered trademark) YH-434L (trade name, manufactured by Toto Kasei Co., Ltd.), EHPE-3150 (trade name) , manufactured by Daicel Corporation), compounds having two or more oxetanyl groups include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (trade names, Toagosei ( (manufactured by Ube Industries, Ltd.), "Ethanachol" (registered trademark) OXBP, and "Ethanachol" OXTP (all trade names, manufactured by Ube Industries, Ltd.), each of which is available from each company.

The thermal crosslinking agent (DI) preferably has a phenolic hydroxyl group in one molecule and a methylol group and/or alkoxymethyl group at both ortho positions of the phenolic hydroxyl group. By having the methylol group and/or the alkoxymethyl group adjacent to the phenolic hydroxyl group, the durability of the cured film can be further improved. Examples of the alkoxymethyl group include, but are not limited to, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

The content of the (DI) thermal crosslinking agent is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, based on 100 parts by mass of the (B-I) alkali-soluble resin. . Further, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less. (DI) When the content of the thermal crosslinking agent is 5 parts by mass or more, the heat resistance of the cured film is improved, and when the content is 50 parts by mass or less, a decrease in elongation of the cured film can be prevented.

The photosensitive resin composition (I) preferably contains a photosensitizer (EI). The photosensitizer (E-I) may be a negative type that is cured by light or a positive type that is solubilized by light, and may include (e-1) a polymerizable unsaturated compound and a photopolymerization initiator, or (e-2) a quinonediazide compound, etc. can be preferably contained.

Examples of the polymerizable unsaturated compound in (e-1) include unsaturated double bond functional groups such as a vinyl group, allyl group, acryloyl group, and methacryloyl group, and/or unsaturated triple bond functional groups such as a propargyl group. Among these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred from the viewpoint of polymerizability. In addition, the number of functional groups contained is preferably 1 to 4 from the viewpoint of stability, and they do not have to be the same group. Furthermore, the compound referred to herein preferably has a molecular weight of 30 to 800. If the molecular weight is in the range of 30 to 800, it has good compatibility with the polymer and the reactive diluent. Specifically, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate. , pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpyrolytide Peridinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6- Examples include tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, and N-vinylcaprolactam. These may be used alone or in combination of two or more.

The photopolymerization initiator in (e-1) means one that initiates polymerization mainly by generating radicals when irradiated with light in the ultraviolet to visible light range. From the viewpoint of being able to use a general-purpose light source and of fast curing properties, known photopolymerization initiators selected from acetophenone derivatives, benzophenone derivatives, benzoin ether derivatives, and xanthone derivatives are preferred. Examples of preferred photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexylphenyl ketone, Isobutylbenzoin ether, benzoin methyl ether, thioxanthone, isopropylthioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( Examples include, but are not limited to, 4-morpholinophenyl)-butanone-1 and the like.

The quinonediazide compound (e-2) is one in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond, one in which the sulfonic acid of quinonediazide is bonded to a polyamino compound through a sulfonamide bond, and a compound in which the sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound through an ester bond. Known examples include those with bonds and/or sulfonamide bonds. All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds do not need to be substituted with quinone diazide, but it is preferable that on average 40 mol% or more of the entire functional groups are substituted with quinone diazide. . By using such a quinonediazide compound, we can create a positive photosensitive resin composition that is sensitive to I-line (wavelength 365 nm), H-line (wavelength 405 nm), and G-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays. Obtainable.

Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisO. C.P. -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industries), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by Asahi Yokuzai Kogyo), 2,6-dimethoxy Methyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol , BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo), novolak resin, etc., but are not limited to these.

Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Examples include, but are not limited to, sulfides.

Further, examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

Among these, it is more preferable that (e-2) the quinonediazide compound contains an ester with a phenol compound and a 5-naphthoquinonediazide sulfonyl group. This allows high sensitivity and higher resolution to be obtained with i-line exposure.

(e-2) The content of the quinonediazide compound is preferably 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the resin of component (BI). By setting the content of the quinonediazide compound within this range, higher sensitivity can be achieved, and photosensitivity can be obtained without inhibiting liquid repellency.

The photosensitive resin composition (I) can contain a colorant (FI). The colorant (F-I) refers to a known organic pigment, inorganic pigment, or dye commonly used in the field of electronic information materials. The colorant (F-I) is preferably an organic pigment and/or an inorganic pigment.

Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, and anthraquinone. Anthraquinone pigments such as pyrimidine, flavanthrone, anthrone, indanthrone, pyrantrone or violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments , quinophthalone pigments, threne pigments, benzofuranone pigments, and metal complex pigments.

Examples of inorganic pigments include black iron oxide, cadmium red, red iron, molybdenum red, molybdate orange, chromium vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, and cobalt. Green, cobalt chrome green, Victoria green, ultramarine, navy blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet or cobalt violet.

Examples of the dye include azo dyes, anthraquinone dyes, fused polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine or polymethine dyes.

Examples of red pigments include Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217, 220, 223, 224, Examples include 226, 227, 228, 240, or 254 (all numerical values are color indexes (hereinafter referred to as "CI" numbers)).

Examples of the orange pigment include Pigment Orange 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, or 71 (all numbers are CI numbers).

Examples of the yellow pigment include Pigment Yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, Examples include 153, 154, 166, 168, or 185 (all numbers are CI numbers).

Examples of the purple pigment include Pigment Violet 19, 23, 29, 30, 32, 37, 40, or 50 (all numbers are CI numbers).
Examples of the blue pigment include Pigment Blue 15, 15:3, 15:4, 15:6, 22, 60, or 64 (all numbers are CI numbers).
Examples of green pigments include Pigment Green 7, 10, 36, and 58 (all numbers are CI numbers).

Examples of the black pigment include black organic pigments and black inorganic pigments. Examples of the black organic pigment include carbon black, benzofuranone-based black pigments (described in International Publication No. 2010/081624), perylene-based black pigments, aniline-based black pigments, and anthraquinone-based black pigments. Among these, benzofuranone-based black pigments and perylene-based black pigments are particularly preferred in that they can provide negative photosensitive resin compositions with better sensitivity. Benzofuranone-based black pigments and perylene-based black pigments have low transmittance in the visible region and high light-shielding properties, while their transmittance in the ultraviolet region is relatively high, which allows chemical reactions to proceed efficiently during exposure. be. The benzofuranone black pigment and the perylene black pigment can also be contained together. Examples of black inorganic pigments include graphite, fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver, oxides, composite oxides, sulfides, nitrides, or Oxynitrides may be mentioned, but carbon black or titanium nitride, which have high light-shielding properties, are preferred.

Examples of dyes include Sumilan, Lanyl (registered trademark) series (all manufactured by Sumitomo Chemical Co., Ltd.), Orasol (registered trademark), Oracet (registered trademark), Filamid (registered trademark), and Irgasperse (registered trademark). ), Zapon, Neozapon, Neptune, Acidol series (all manufactured by BASF Corporation), Kayaset (registered trademark), Kayakalan (registered trademark) series (all manufactured by Nippon Kayaku Co., Ltd.), Valifast ( Colors series (manufactured by Orient Chemical Industry Co., Ltd.), Savinyl, Sandoplast, Polysynthren (registered trademark), Lanasyn (registered trademark) series (all manufactured by Clariant Japan Co., Ltd.), Aizen (registered trademark), Spilon (registered trademark) series (all manufactured by Hodogaya Chemical Industry Co., Ltd.), functional pigments (manufactured by Yamada Chemical Industry Co., Ltd.), Plast Color, Oil Color series (manufactured by Arimoto Chemical Industry Co., Ltd.) etc. can be mentioned.

For the purpose of improving the contrast of an organic EL display device, the colorant is preferably black, which can block visible light over the entire wavelength range, and at least one selected from organic pigments, inorganic pigments, and dyes is used. A coloring agent that exhibits a black color when formed into a cured film may be used. For that purpose, the above-mentioned black organic pigment and black inorganic pigment may be used, or two or more types of organic pigments and dyes may be mixed to create a pseudo-black color. In the case of pseudo-blackening, it can be obtained by mixing two or more of the above-mentioned red, orange, yellow, purple, blue, green, and other organic pigments and dyes. Note that the photosensitive resin composition (I) itself does not necessarily have to be black, and a coloring agent that changes color during heat curing so that the cured film exhibits a black color may be used.

Among these, from the viewpoint of ensuring high heat resistance, it is preferable to use a coloring agent that contains an organic pigment and/or an inorganic pigment and exhibits a black color when formed into a cured film. Further, from the viewpoint of ensuring high insulation properties, it is preferable to use a coloring agent that contains an organic pigment and/or dye and exhibits a black color when formed into a cured film. That is, from the viewpoint of achieving both high heat resistance and insulation, it is preferable to use a coloring agent that contains an organic pigment and exhibits a black color when formed into a cured film.

The content of the colorant (F-I) is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and even more preferably 30 parts by weight or more, based on 100 parts by weight of the component (B-I). Preferably it is 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less. When the content of the colorant is 10 parts by mass or more, the coloring properties required for the cured film can be obtained, and when the content is 300 parts by mass or less, storage stability is improved.

When a pigment is used as the colorant (FI), the photosensitive resin composition (I) preferably contains a dispersant. By containing the dispersant, the colorant can be uniformly and stably dispersed in the resin composition. The dispersant is not particularly limited, but a polymer dispersant is preferred. Examples of the polymer dispersant include a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a polyallylamine polymer dispersant, and a carbodiimide polymer dispersant. More specifically, a polymeric dispersant has a main chain consisting of polyamino, polyether, polyester, polyurethane, polyacrylate, etc., and has an amine, carboxylic acid, phosphoric acid, amine salt, or carboxylic acid at the side chain or main chain terminal. Refers to polymeric compounds with polar groups such as acid salts and phosphates. The polar group is adsorbed onto the pigment, and the steric hindrance of the main chain polymer plays a role in stabilizing the dispersion of the pigment.

The dispersant can be a (polymer) dispersant that has only an amine value, a (polymer) dispersant that has only an acid value, a (polymer) dispersant that has an amine value and an acid value, or a (polymer) dispersant that has both an amine value and an acid value. Although it is classified as a (polymer) dispersant that does not have an amine value, a (polymer) dispersant that has an amine value and an acid value, and a (polymer) dispersant that has only an amine value are preferable. Molecular) dispersants are more preferred.

Specific examples of polymer dispersants having only an amine value include DISPERBYK (registered trademark) 102, 160, 161, 162, 2163, 164, 2164, 166, 167, 168, 2000, 2050, 2150, 2155, 9075, 9077, BYK-LP N6919, BYK-LP N21116 or BYK-LP N21234 (all manufactured by BYK Chemie), EFKA (registered trademark) 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300 , 4330, 4340, 4400, 4401, 4402, 4403 or 4800 (all manufactured by BASF), Ajisper (registered trademark) PB711 (manufactured by Ajinomoto Fine Techno) or SOLSPERSE (registered trademark) 13240, 13940, 20000, 71000 or 76500 (both manufactured by Lubrizol).

The ratio of the dispersant to the colorant is preferably 1% by mass or more, more preferably 3% by mass or more, in order to improve dispersion stability while maintaining heat resistance. Further, it is preferably 100% by mass or less, more preferably 50% by mass or less.

The photosensitive resin composition (I) preferably contains an organic solvent (GI). Examples of the organic solvent (GI) include compounds such as ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.

More specifically, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-butyl ether, tripropylene glycol Ethers such as monomethyl ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate ( (hereinafter referred to as "PGMEA"), dipropylene glycol methyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate or 1,6-hexane Acetates such as diol diacetate, ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone, lactic acid alkyl esters such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate, 2-hydroxy-2- Ethyl methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate , 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i- acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, Other esters such as methyl acetoacetate, ethyl acetoacetate or ethyl 2-oxobutanoate, aromatic hydrocarbons such as toluene or xylene, N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, etc. or alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol or diacetone alcohol. Can be mentioned.

When a pigment is used as the colorant (FI), it is preferable to use an acetate compound as the organic solvent (GI) in order to stabilize the dispersion of the pigment. The proportion of acetate compounds in all the organic solvents (GI) contained in the photosensitive resin composition (I) is preferably 50% by mass or more, more preferably 70% by mass or more. Further, it is preferably 100% by mass or less, more preferably 90% by mass or less.

The amount of the solvent to be used is not particularly limited as it varies depending on the required film thickness and the coating method employed, but it is preferably 50 to 2000 parts by mass based on 100 parts by mass of the resin of component (B-I). , particularly preferably 100 to 1500 parts by mass.

The photosensitive resin composition (I) may optionally contain a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, and methyl to improve wettability with the substrate. It may contain ketones such as isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.

Photosensitive resin composition (I) can contain an adhesion improver. Examples of adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy group containing Examples include compounds obtained by reacting silicon compounds. Two or more types of these may be contained. By containing these adhesion improvers, when developing a photosensitive resin film, it is possible to improve the adhesion with an underlying base material such as a silicon wafer, ITO, SiO2, silicon nitride, etc. Furthermore, resistance to oxygen plasma used for cleaning and UV ozone treatment can be increased. The content of the adhesion improver is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, based on 100 parts by mass of component (BI). Further, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

The photosensitive resin composition (I) may contain a surfactant, if necessary, for the purpose of improving wettability with the substrate. Commercially available compounds can be used as the surfactant. Specifically, silicone surfactants include the SH series, SD series, and ST series from Dow Corning Toray Silicone, the BYK series from BYK Chemie Japan, and Shin-Etsu Silicone. Examples of fluorine-based surfactants include Dainippon Ink Industries' Megafac (registered trademark) series, Sumitomo 3M's Florado series, and Asahi Glass Co., Ltd.'s KP series and Toshiba Silicone's TSF series. "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series, Shin-Akita Kasei Co., Ltd.'s EF series, Omnova Solutions Co., Ltd.'s Polyfox series, etc. Examples of the surfactant include, but are not limited to, the Polyflow series manufactured by Kyoeisha Chemical Co., Ltd. and the "Disparon (registered trademark)" series manufactured by Kusumoto Kasei Co., Ltd.

The content of the surfactant is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, based on 100 parts by mass of component (BI). Further, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.

Next, a method for producing photosensitive resin composition (I) will be explained. For example, the photosensitive resin composition (I) can be obtained by dissolving the components (AI) to (EI) above in an organic solvent (GI). Examples of the dissolution method include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually from room temperature to 80°C. Further, the order of dissolving each component is not particularly limited, and for example, there is a method of dissolving compounds in order starting from the one with the lowest solubility.

The obtained photosensitive resin composition (I) is preferably filtered using a filter to remove dust and particles. Examples of filter pore diameters include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, and 0.05 μm. Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and it is preferable to use polyethylene or nylon for filtration.

Next, a method for producing a cured film using photosensitive resin composition (I) will be described in detail.

The method for manufacturing the cured film is
(1) a step of applying the photosensitive resin composition (I) to a substrate to form a photosensitive resin film;
(2) a pre-bake step of drying the photosensitive resin film;
(3) an exposure step in which the dried photosensitive resin film is irradiated with actinic radiation through a photomask;
The process includes (4) a developing step of developing the exposed photosensitive resin film, and (5) a step of heating the developed photosensitive resin film to form a cured film, in this order.

In the step of forming a photosensitive resin film, the photosensitive resin composition (I) is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc. A photosensitive resin film is obtained. Prior to coating, the substrate to which the photosensitive resin composition (I) is applied may be pretreated with the adhesion improver described above. For example, a solution in which 0.5 to 20% by mass of the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. is used. Examples include methods of treating the surface of the base material. Examples of methods for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

In the pre-baking process for drying the photosensitive resin film, the applied photosensitive resin film is subjected to vacuum drying treatment as necessary, and then dried at a temperature of 50°C to 180°C using a hot plate, oven, infrared rays, etc. A dry photosensitive resin film is obtained by heat treatment for a period of minutes to several hours.

Next, a process of exposing the dried photosensitive resin film to light through a photomask will be described. Actinic radiation is irradiated onto the photosensitive resin film through a photomask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays, but in the present invention, it is preferable to use I-lines (365 nm), H-lines (405 nm), and G-lines (436 nm) from a mercury lamp. . After irradiating with actinic radiation, a post-exposure bake may be performed. By performing post-exposure baking, effects such as improved resolution after development or increased allowable range of development conditions can be expected. For post-exposure baking, an oven, hot plate, infrared rays, flash annealing device, laser annealing device, or the like can be used. The post-exposure bake temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure bake time is preferably 10 seconds to several hours. When the post-exposure bake time is within the above range, the reaction proceeds favorably and the development time may be shortened.

In the development step of developing the exposed photosensitive resin film, the exposed photosensitive resin film is developed using a developer to remove areas other than the exposed areas. As a developer, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl Aqueous solutions of alkaline compounds such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine are preferred. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination. good. As the developing method, methods such as spray, paddle, immersion, and ultrasonic waves are possible.

Next, the pattern formed by development is preferably rinsed with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may be added to distilled water for rinsing.

Next, a cured film is obtained by heat-treating the developed photosensitive resin film. Since residual solvent and components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. Furthermore, when a thermal crosslinking agent (DI) is contained, the thermal crosslinking reaction can be advanced by heat treatment, and the heat resistance and chemical resistance can be improved. This heat treatment is carried out by selecting a temperature and increasing the temperature stepwise, or by selecting a certain temperature range and increasing the temperature continuously for 5 minutes to 5 hours. For example, heat treatment is performed at 150° C. and 250° C. for 30 minutes each. Alternatively, a method may be used in which the temperature is linearly raised from room temperature to 300° C. over 2 hours. The heat treatment conditions in the present invention are preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher. The heat treatment conditions are preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower.

Next, a method for producing a cured film using a photosensitive sheet formed from the photosensitive resin composition (I) will be described. Note that here, the photosensitive sheet is defined as a sheet obtained by coating the photosensitive resin composition (I) on a releasable base material and drying it.

When using a photosensitive sheet formed from the photosensitive resin composition (I), if the photosensitive sheet has a protective film, this is peeled off, the photosensitive sheet and the substrate are faced, and bonded together by thermocompression bonding. , to obtain a photosensitive resin film. The photosensitive sheet can be obtained by coating the photosensitive resin composition (I) on a support film made of polyethylene terephthalate or the like as a releasable base material and drying the coating.

The thermocompression bonding can be performed by heat press treatment, heat lamination treatment, heat vacuum lamination treatment, or the like. The bonding temperature is preferably 40° C. or higher from the viewpoint of adhesion to the substrate and embeddability. Further, when the photosensitive sheet has photosensitivity, the bonding temperature is preferably 140° C. or lower in order to prevent the photosensitive sheet from curing during bonding and reducing the resolution of pattern formation in the exposure and development steps.

The photosensitive resin film obtained by bonding the photosensitive sheet to the substrate is produced by following the steps of exposing the photosensitive resin film, developing the exposed photosensitive resin film, and curing with heat. A cured film can be formed.

A cured film obtained by curing the photosensitive resin composition (I) or a photosensitive sheet (hereinafter sometimes referred to as the second embodiment of the cured film of the present invention) can be used for organic EL display devices, semiconductor devices, multilayer wiring boards, etc. Can be used for electronic components. Specifically, insulating layers of organic EL elements, planarization layers of substrates with drive circuits of display devices using organic EL elements, interlayer insulating films between rewirings of semiconductor devices or semiconductor components, passivation films of semiconductors, and semiconductors. Suitable for applications such as protective films for devices, interlayer insulation films for multilayer wiring for high-density packaging, wiring protection insulation layers for circuit boards, on-chip microlenses for solid-state imaging devices, and flattening layers for various displays and solid-state imaging devices. It will be done. Examples of electronic devices having a surface protective film, interlayer insulating film, etc. in which the second embodiment of the cured film of the present invention is arranged include MRAMs with low heat resistance. That is, the second embodiment of the cured film of the present invention is suitable for use as a surface protective film for MRAM. Further, a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, specifically, a display such as an LCD, an ECD, an ELD, an organic EL, etc. It can be used as an insulating layer of devices. Hereinafter, an explanation will be given using an organic EL display device as an example.

An organic EL display device comprising a cured film of photosensitive resin composition (I) has a drive circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and the insulating layer The layer comprises the second embodiment of the cured film of the present invention. Taking an active matrix display device as an example, it has a TFT on a substrate such as glass or a resin film, and wiring located on the side of the TFT and connected to the TFT, and covering unevenness on top of the TFT. In this manner, a flattening layer is provided, and a display element is further provided on the flattening layer. The display element and the wiring are connected through contact holes formed in the planarization layer.

An organic EL display device comprising a cured film of the photosensitive resin composition (I) is preferably used when a manufacturing method is used in which at least a part of a pixel surrounded by the cured film is formed by an inkjet method. be done. By using a cured film obtained by curing the photosensitive resin composition (I) or a photosensitive resin sheet, it has liquid repellency and prevents the ejected liquid used in the inkjet method from entering into adjacent pixels. Therefore, an organic EL display device with less occurrence of display defects and excellent durability can be obtained.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Note that Example 15 and Example 27 are referred to as Reference Example 15 and Reference Example 27, respectively. First, the measurement method and evaluation method will be explained.

(1) Average molecular weight measurement The molecular weights of (a1) to (a8) and (c1) to (c2) used in the examples were measured using a GPC (gel permeation chromatography) device Waters 2690-996 (manufactured by Nippon Waters Co., Ltd.). was used, the developing solvent was tetrahydrofuran (hereinafter referred to as THF), and the weight average molecular weight (Mw) was calculated in terms of polystyrene.

In addition, the molecular weights of (b1) to (b4) used in the examples were measured using the above-mentioned GPC device using N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a developing solvent, and were calculated as number averages in terms of polystyrene. Molecular weight (Mn) was calculated.

(2) Film thickness measurement Using a surface roughness/contour measuring machine (SURFCOM1400D; Tokyo Seimitsu Co., Ltd.), the measurement magnification was 10,000 times, the measurement length was 1.0mm, and the measurement speed was 0.30mm/ As s, the film thickness was measured after prebaking, after development, and after curing.

(3) Evaluation of contact angle To measure the contact angle, 1 μL of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) was dropped onto the partition pattern formed on the substrate by the method described below, and the contact angle was measured. . The measurement was performed using a contact angle measuring device DMs-401 (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) using a sessile drop method at 23° C. in accordance with JIS-R3257.

The measurement results of the PGMEA contact angle on the cured film are determined as follows: the contact angle is 60° or more (A+), the contact angle is 50° or more and less than 60° (A), and the contact angle is 40° or more and less than 50°. A contact angle of less than 30° (B) was considered excellent, a contact angle of 30° or more and less than 40° (C) was considered good, and a contact angle of less than 30° (D) was considered poor.
A+: Contact angle is 60° or more A: Contact angle is 50° or more and less than 60° B: Contact angle is 40° or more and less than 50° C: Contact angle is 30° or more and less than 40° D: Contact angle is less than 30°.

(4) Evaluation of ink wettability of openings Using a substrate on which the partition pattern 5 to be treated later is formed, an ink of a compound (HT-1) using methyl benzoate as a solvent is applied as a hole injection layer to an inkjet device ( Using Litlex 142 (manufactured by ULVAC), the number of ink droplets required to coat the entire opening was counted when dropping the ink into the area surrounded by the partition wall. The volume per drop of ink used in this evaluation was 15 pl.

(5) Evaluation of display defect occurrence rate The organic EL display device manufactured by the method described below is driven by direct current at 10 mA/cm ² to emit light, and it is observed whether there are any display defects such as a non-emitting area in the center of the pixel. Of the 20 organic EL display devices, the display defect occurrence rate was calculated from the number of devices that emitted light normally.

Judgment is made as shown below. If the display defect occurrence rate is 30% or more and less than 40% (C), it is passed; if the display defect occurrence rate is 20% or more and less than 30% (B), it is considered good, and the display defect occurrence rate is less than 20%. (A and A+) were considered excellent.
A+: Display defect rate is 0% or more and less than 10% A: Display defect rate is 10% or more and less than 20% B: Display defect rate is 20% or more and less than 30% C: Display defect rate is 30% or more and less than 30% Less than % D: Display defect occurrence rate is 40% or more and less than 70% E: Display defect occurrence rate is 70% or more and less than 100% (6) Evaluation of durability The organic EL display device manufactured by the method described below was heated at 80°C After holding it for 100 hours, it was driven to emit light at 10 mA/cm ² with direct current drive, and it was observed whether there were any display defects such as non-emitting areas in the center of the pixel.The incidence of display defects was calculated in the same way as above, and the durability was evaluated. The sex was determined.
A+: Display defect rate is 0% or more and less than 10% A: Display defect rate is 10% or more and less than 20% B: Display defect rate is 20% or more and less than 30% C: Display defect rate is 30% or more and less than 30% Less than % D: Display defect occurrence rate is 40% or more and less than 70% E: Display defect occurrence rate is 70% or more and less than 100% Compounds used in Examples and Comparative Examples are shown below.

Synthesis Example 1 Synthesis of Compound (AI) and Liquid Repellent Material (A) 100 parts by mass of cyclohexanone was placed in a 1000 mL reaction vessel equipped with a stirring device, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet. In addition, the temperature was raised to 110° C. under a nitrogen gas atmosphere. The temperature of cyclohexanone was maintained at 110° C., and the monomer mixed solutions shown in Table 1 were added dropwise at a constant rate over 2 hours using a dropping funnel to prepare each monomer solution. After the dropwise addition was completed, the monomer solution was heated to 115° C. and reacted for 2 hours to obtain copolymers (a1) to (a9). The weight average molecular weight was determined using GPC. The results are shown in Table 1.
The abbreviations in Table 1 are shown below.
DMAA: N,N-dimethylacrylamide FAMAC-6: 2-(perfluorohexyl)ethyl methacrylate GMA: Glycidyl methacrylate Karenz MOI-BM: 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was mixed with 100 mL of acetone and 17 mL of propylene oxide. .4 g (0.3 mol) and cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise thereto. After the dropwise addition was completed, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and dried under vacuum at 50°C.

30 g of the 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 here using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon did not deflate any further, and the reaction was terminated. After the reaction was completed, the catalyst was filtered to remove the palladium compound, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 3 Synthesis of alkali-soluble resin (b1) Under a stream of dry nitrogen, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was mixed with N -Methyl-2-pyrrolidone (hereinafter referred to as NMP) was dissolved in 500 g. 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 2 was added thereto together with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as an end-capping agent was added together with 50 g of NMP, and the mixture was reacted at 50° C. for 2 hours. Thereafter, 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal was added. After the addition, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then poured into 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the desired polyimide precursor (b1). The number average molecular weight of the polyimide precursor (b1) was 11,000.

Synthesis Example 4 Synthesis of alkali-soluble resin (b2) Under a stream of dry nitrogen, 58.6 g (0.16 mol) of BAHF and 8.7 g (0.08 mol) of 3-aminophenol as an end capping agent were mixed with N-methyl-2. -Dissolved in 300g of pyrrolidone (NMP). 62.0 g (0.20 mol) of ODPA was added thereto along with 100 g of NMP, and the mixture was stirred at 20°C for 1 hour, and then at 50°C for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while water was azeotroped with the xylene. After the stirring was completed, the solution was poured into 5 L of water and a 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 the target polyimide (b2). The number average molecular weight of polyimide (b2) was 8,200.

Synthesis Example 5 Synthesis of alkali-soluble resin (b3) Under a stream of dry nitrogen, 41.3 g (0.16 mol) of diphenyl ether-4,4'-dicarboxylic acid and 43.3 g (0.16 mol) of 1-hydroxy-1,2,3-benzotriazole were mixed. 0.16 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 2 g (0.32 mol) with 73.3 g (0.20 mol) of BAHF was dissolved in 570 g of NMP, and then reacted at 75° C. for 12 hours. Next, 13.1 g (0.08 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water/methanol=3/1 (volume ratio) to obtain a white precipitate. 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 the desired polybenzoxazole (PBO) precursor (b3). The number average molecular weight of the PBO precursor (b3) was 8,500.

Synthesis Example 6 Synthesis of alkali-soluble resin (b4) A methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio 30/40/30) was synthesized by a known method (Japanese Patent No. 3120476; Example 1). By adding 40 parts by mass of glycidyl methacrylate to 100 parts by mass of the copolymer, reprecipitating with purified water, filtering and drying, a radically polymerizable monomer with a number average molecular weight of 10,000 and an acid value of 110 (mgKOH/g) is obtained. An acrylic resin (b4) which is a polymer containing the following was obtained.

Synthesis Example 7 Synthesis of phenolic resin (c1) Under a stream of dry nitrogen, 108.0 g (1.00 mol) of m-cresol, 75.5 g of a 37% by mass formaldehyde aqueous solution (0.93 mol of formaldehyde), oxalic acid dihydrate After charging 0.63 g (0.005 mol) and 264 g of methyl isobutyl ketone, it was immersed in an oil bath and a polycondensation reaction was carried out for 4 hours while the reaction solution was refluxed. After that, the temperature of the oil bath was raised over 3 hours, and then the pressure inside the flask was reduced to 4.0 kPa to 6.7 kPa to remove volatile components, and the dissolved resin was cooled to room temperature. Thus, a novolac type phenol resin (c1) was obtained. The weight average molecular weight was found to be 3,500 by GPC.

Synthesis Example 8 Synthesis of quinonediazide compound (e2) Under a stream of dry nitrogen, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g of 5-naphthoquinonediazide sulfonyl acid chloride (0.135 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not rise above 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound (e2) represented by the following formula.

Below, abbreviations of components used in Examples are shown.
<(A) Liquid repellent material>
"Megafac (registered trademark)" RS-72-K (liquid repellent material containing a polymer of the chemical formula below as a compound having a urethane group and a structure represented by general formula (13), manufactured by DIC Corporation)

<(DI) and (D) thermal crosslinking agent>
HMOM-TPHAP; (a compound having a phenolic hydroxyl group and having substituents with a molecular weight of 40 or more at both ortho positions of the phenolic hydroxyl group, shown in the chemical formula below, manufactured by Honshu Kagaku Kogyo Co., Ltd.)

VG3101L: "Tecmore" (registered trademark) VG3101L (compound shown by the chemical formula below, manufactured by Printec Co., Ltd.).

<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate PGME; Propylene glycol monomethyl ether GBL; γ-butyrolactone.

Examples 1 to 27, Comparative Examples 1 to 7
FIG. 2 shows a schematic diagram of the substrate used for evaluation. First, a 10 nm thick ITO transparent conductive film was formed on the entire surface of a 38×46 mm alkali-free glass plate 1 by sputtering and etched as a first electrode 2 . Further, an auxiliary electrode 3 was also formed at the same time in order to take out the second electrode. The obtained substrate was ultrasonically cleaned for 10 minutes using "Semico Clean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.), washed with ultrapure water, and dried to obtain a substrate.

Next, each component was mixed at the compounding ratio shown in Tables 2 and 3 under a yellow light, and sufficiently stirred at room temperature to dissolve. Thereafter, the obtained solution was filtered through a filter with a pore size of 1 μm to obtain photosensitive resin compositions W1 to W34. Using the obtained photosensitive resin composition, it was applied onto this substrate by a spin coating method and prebaked on a hot plate at 120° C. for 4 minutes to form a dry coating film, and then a photomask having a predetermined pattern was formed. After patterning exposure through a 2.38% TMAH aqueous solution, it is developed for 60 seconds or 120 seconds to dissolve unnecessary parts, and then rinsed with pure water to create an opening with a width of 70 μm and a length of 260 μm on the substrate. Similarly to the partition pattern 4 in which the openings were arranged in one place in the center, openings with a width of 70 μm and a length of 260 μm were arranged on the substrate at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction. , a partition wall pattern 5 having a shape in which each opening exposed the first electrode was formed.

Next, the barrier rib pattern 4 with one opening in the center and the substrate with the barrier rib pattern 5 formed thereon were heated at 250° C. in a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere. (3) Evaluation of the contact angle was performed using a substrate on which a barrier rib pattern 4 was formed by heating for 1 hour to cure the substrate, and a partition pattern 4 was formed with one opening in the center. The results are shown in Tables 4 and 5.

Next, using the substrate on which the barrier rib pattern 5 was formed by developing with a 2.38% TMAH aqueous solution for 60 seconds, an ink of a compound (HT-1) using methyl benzoate as a solvent was applied as a hole injection layer by an inkjet jet. Using a device (Litlex 142 manufactured by ULVAC), the ink was dropped onto the area surrounded by the partition wall, and (4) evaluation of ink wettability of the opening was performed. Thereafter, it was fired at 200°C to form a hole injection layer. Next, as a hole transport layer, a compound (HT-2) using 4-methoxytoluene as a solvent was dropped into the area surrounded by the partition walls using an inkjet device, and then baked at 190°C to form a hole transport layer. A transport layer was formed. Furthermore, as a light-emitting layer, a mixture of Compound (GH-1) and Compound (GD-1) using 4-methoxytoluene as a solvent was dropped onto the area surrounded by the partition walls using an inkjet device, and then heated to 130°C. A light-emitting layer was formed. Thereafter, a compound (ET-1) and a compound (LiQ) were sequentially laminated as electron transport materials by a vacuum evaporation method at a volume ratio of 1:1 to form an organic EL layer 6. Next, a compound (LiQ) was deposited to a thickness of 2 nm, and then Mg and Ag were deposited to a thickness of 10 nm at a volume ratio of 10:1 to form the second electrode 7. Finally, a cap-shaped glass plate was adhered using an epoxy resin adhesive under a low-humidity nitrogen atmosphere for sealing, and four 5 mm square light emitting devices were fabricated on one substrate.

The organic EL display device produced by the method described above was caused to emit light by direct current driving at 10 mA/cm ² , and (5) the display defect occurrence rate was evaluated. Furthermore, the temperature was maintained at 80°C for 100 hours, and then the light was emitted again by direct current drive at 10 mA/cm ² to confirm whether there was any change in the light emitting characteristics. (6) The results of the durability evaluation are shown in Tables 4 and 5. show.

In this way, it was confirmed that the organic EL light emitting device has high durability, with few occurrences of display defects and maintaining its performance as a light emitting device even after a durability test under accelerated conditions.

Examples 28-34
FIG. 2 shows a schematic diagram of the substrate used for evaluation. First, a 10 nm thick ITO transparent conductive film was formed on the entire surface of a 38×46 mm alkali-free glass plate 1 by sputtering and etched as a first electrode 2 . Further, an auxiliary electrode 3 was also formed at the same time in order to take out the second electrode. The obtained substrate was ultrasonically cleaned for 10 minutes using "Semico Clean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.), washed with ultrapure water, and dried to obtain a substrate.

Next, photosensitive resin composition W21 was applied onto this substrate by spin coating, and prebaked for 4 minutes on a hot plate at 120° C. to form a dry coating film. Thereafter, patterning exposure was performed through a photomask having a predetermined pattern. At this time, due to the "half exposure", a step shape is formed, which has a first partition part having a trapezoidal cross section and a second partition part having a trapezoidal cross section above the first partition part. When the width of the top surface of the first partition wall is A and the width of the bottom surface of the second partition wall is B on a surface cut in the vertical direction, exposure is performed so that a step shape that satisfies the relationship A>B is formed. I did it.

Next, the substrate was developed with a 2.38% TMAH aqueous solution for 60 seconds to dissolve unnecessary parts, and then rinsed with pure water. Two partition wall patterns 5 were formed which were arranged at a pitch of 465 μm in the length direction and each opening exposed the first electrode. Table 6 shows the thickness of the partition walls that were created.

Next, using the substrate on which the partition pattern 5 was formed, ink of a compound (HT-1) using methyl benzoate as a solvent was applied to the partition walls using an inkjet device (Litlex 142 manufactured by ULVAC) as a hole injection layer. Dropped into the area surrounded by. At this time, the presence or absence of ink leakage outside the opening was checked and evaluated as follows.

A: No ink leakage B: Ink leakage Next, baking was performed at 200° C. to form a hole injection layer. Thereafter, the cross section of the opening was observed using a SEM using the first substrate, and the position of the end of the hole injection layer was confirmed. It was evaluated as follows.

A: The end of the hole injection layer is on the side surface of the second partition wall.

B: The end of the hole injection layer is on the side surface of the first partition wall.

Next, as a hole transport layer on the other substrate, a compound (HT-2) using 4-methoxytoluene as a solvent was dropped onto the area surrounded by the partition walls using an inkjet device, and then heated at 190°C. This was fired to form a hole transport layer. Furthermore, as a light-emitting layer, a mixture of Compound (GH-1) and Compound (GD-1) using 4-methoxytoluene as a solvent was dropped onto the area surrounded by the partition walls using an inkjet device, and then heated to 130°C. A light-emitting layer was formed. Thereafter, a compound (ET-1) and a compound (LiQ) were sequentially laminated as electron transport materials by a vacuum evaporation method at a volume ratio of 1:1 to form an organic EL layer 6. Next, a compound (LiQ) was deposited to a thickness of 2 nm, and then Mg and Ag were deposited to a thickness of 10 nm at a volume ratio of 10:1 to form the second electrode 7. Finally, a cap-shaped glass plate was adhered using an epoxy resin adhesive under a low-humidity nitrogen atmosphere for sealing, and four 5 mm square light emitting devices were fabricated on one substrate.

The organic EL display device produced by the above method was driven to emit light at 10 mA/cm ² with direct current drive, and the center and outer periphery of the pixel were compared to observe the presence or absence of brightness unevenness within the pixel for evaluation.

A: Comparing the center and outer periphery of the pixel, there is no display defect.

B: Comparing the center and outer periphery of the pixel, there is a display defect.

1 Alkali-free glass plate 2 First electrode 3 Auxiliary electrode 4 Partition pattern 5 with one opening in the center Partition pattern 6 Organic EL layer 7 Second electrode 8 Substrate 9 First partition part 10 Second partition part 11 Function Layer 12 Functional layer end

Claims (18)

A photosensitive resin composition containing a liquid repellent material (A) having at least an amide group or a urethane group, an alkali-soluble resin (B), and a photosensitizer (E),
Furthermore, it contains at least one resin (C) selected from the group consisting of phenol resin and polyhydroxystyrene resin,
The alkali-soluble resin (B) contains at least one alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof,
The liquid repellent material (A) having at least an amide group or a urethane group contains a structural unit represented by the following general formula (2) or a compound having a structure represented by the following general formula (13),
The photosensitizer (E) contains (e-2) a quinonediazide compound,
Photosensitive, wherein the total amount of at least one resin (C) selected from the group consisting of the phenol resin and polyhydroxystyrene resin is 10 to 100 parts by mass based on 100 parts by mass of the alkali-soluble resin (B). Resin composition.

(In general formula (2), R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, R ⁵ represents an aliphatic group having 1 to 6 carbon atoms, and R ⁶ represents a C 3 to 6 aliphatic group. (Represents a perfluoroalkyl group.)

(In general formula (13), X is selected from the following structural formulas (a) to (e), and all Xs may have the same structure, or multiple structures may exist randomly or in a block shape. Good. m is an integer from 1 to 100 representing the number of repeating units.)

The photosensitive resin composition according to claim 1, wherein the liquid repellent material (A) having at least an amide group or a urethane group contains a compound having a structural unit represented by the following general formula (1) or the following general formula (11). thing.

(In general formula (1), R ¹ , R ² and R ³ represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.)

(In general formula (11), R ¹⁸ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and R ¹⁹ represents an aliphatic group having 1 to 6 carbon atoms. A represents the following formula (A-1) Or represents a urethane group represented by (A-2).)

The liquid repellent material (A) having at least an amide group or a urethane group includes a structural unit represented by general formula (11) and a compound having a structure represented by general formula (13). Photosensitive resin composition. The liquid repellent material (A) having at least an amide group or a urethane group has a structure in which the sum of the structural units represented by general formula (1) or general formula (11) constitutes the liquid repellent material (A). The photosensitive resin composition according to claim 2 or 3, wherein the amount is in the range of 15 to 85 mol%. The photosensitive resin compound according to claim 1, wherein the liquid repellent material (A) having at least an amide group or a urethane group further has an epoxy group. Any one of claims 1 to 5, wherein the content of the liquid repellent material (A) having at least an amide group or a urethane group is 0.1 to 10 parts by mass based on 100 parts by mass of the alkali-soluble resin (B). A photosensitive resin compound described in Crab. The photosensitive resin composition according to any one of claims 1 to 6 , further comprising a thermal crosslinking agent (D). The photosensitive resin composition according to any one of claims 1 to 7 , further comprising a colorant (F). A cured film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 8 . A display device having a grid-like partition wall formed on a substrate,
The partition wall includes a cured film made of a cured product of a photosensitive resin composition ,
The photosensitive resin composition contains a liquid repellent material (A) having at least an amide group or a urethane group, an alkali-soluble resin (B), and a photosensitizer (E),
The alkali-soluble resin (B) contains at least one alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof,
The liquid repellent material (A) having at least an amide group or a urethane group contains a structural unit represented by the following general formula (2) or a compound having a structure represented by the following general formula (13),
A display device in which the photosensitizer (E) contains (e-2) a quinonediazide compound .

(In general formula (2), R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, R ⁵ represents an aliphatic group having 1 to 6 carbon atoms, and R ⁶ represents a C 3 to 6 aliphatic group. (Represents a perfluoroalkyl group.)

(In general formula (13), X is selected from the following structural formulas (a) to (e), and all Xs may have the same structure, or multiple structures may exist randomly or in a block shape. Good. m is an integer from 1 to 100 representing the number of repeating units.)

The lattice-shaped partition formed on the substrate includes a first partition having a trapezoidal cross section cut perpendicularly to the longitudinal direction of the partition and the surface of the substrate, and a first partition that crosses an upper part of the first partition. It has a stepped shape having a trapezoidal surface and a second partition wall, and in the cross section, if the width of the top surface of the first partition wall is A, and the width of the bottom surface of the second partition wall is B, then A The display device according to claim 10 , which satisfies the relationship >B. 12. The display device according to claim 11, wherein the partition wall has a thickness of 0.5 to 5.0 μm, and the first partition wall has a thickness of 0.1 to 1.0 μm. The display device according to claim 11 or 12 , wherein the first partition wall portion and the second partition wall portion are formed from a cured film of the same material. A display device according to any one of claims 10 to 13 , wherein a functional layer is formed in a region surrounded by partition walls. 15. The display device according to claim 14 , wherein an end of the functional layer is located on a side surface of the second partition in a cross section cut perpendicular to the longitudinal direction of the partition and the surface of the substrate. An organic EL display device according to claim 14 or 15, wherein the functional layer of the display device contains at least one kind selected from the group consisting of an organic EL light-emitting material, a hole-injecting material, and a hole-transporting material. A method for manufacturing a substrate with partition walls, comprising the following steps (1) to (4) in this order.
(1) Step of applying the photosensitive resin composition according to any one of claims 1 to 8 on a substrate having a first electrode to form a photosensitive resin film. (2) Exposing the photosensitive resin film to light. Step (3) Step of developing the exposed photosensitive resin film (4) Step of forming partition walls by heat treating the developed photosensitive resin film A method for manufacturing a display device comprising the following steps (5) to (6) in this order.
(5) In a partition-equipped substrate having partition walls containing a cured product of the photosensitive resin composition according to any one of claims 1 to 8 , a functional ink is applied in an area surrounded by the partition walls by an inkjet. Step of forming a functional layer (6) Step of forming a second electrode on the functional layer

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