Negative photosensitive composition, cured film, organic EL display device, and method for producing the cured film

Abstract

Provided is a negative-type photosensitive composition that enables image development to take place using a low-concentration inorganic alkaline aqueous solution, and that enables formation of a pixel division layer that achieves both a small taper angle and a low drive voltage for an organic EL display device. This negative-type photosensitive composition contains: (a) at least one selected from the group consisting of (meth)acrylate compounds having one 9,9-bisarylfluorene skeleton in the molecule and having a structure represented by formula (1) in the molecule, (meth)acrylate compounds having one or two adamantane skeletons in the molecule and having a structure represented by formula (1) in the molecule, and salts thereof; and (b) a photoinitiator.

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive composition, a cured film, an organic EL display device, and a method for producing the cured film. [Background technology]

[0002] Many products equipped with organic electroluminescence (EL) display devices have been developed, including smartphones, televisions, and in-car monitors. Organic EL display devices are self-emitting devices that emit light using energy generated by the recombination of electrons injected from the cathode and holes injected from the anode, and each emitting pixel, such as red, blue, green, or white, is formed in the openings of a patterned pixel division layer that also functions as an insulating layer.

[0003] In recent years, in order to improve the visibility and contrast of organic electroluminescent (EL) display devices, techniques have been attracting attention for blackening pixel division layers to impart light-blocking properties, thereby suppressing color mixing due to light leakage into adjacent light-emitting pixels and reflection of external light such as sunlight. Patent Document 1 discloses, for example, a negative-type photosensitive composition containing a (meth)acrylate compound having a fluorene or indane skeleton, a polyimide resin, and a black pigment as a material for forming the pixel division layer. Patent Document 1 claims that a pixel division layer having both high light-blocking properties and a low taper angle can be formed. Furthermore, the use of fluorene-based photopolymerizable compounds has also been proposed in the field of interlayer insulating films for liquid crystal display devices. For example, Patent Document 2 discloses a negative-type photosensitive composition containing an acrylate compound having a fluorene skeleton and a styrene / acrylic resin, but not containing a pigment. On the other hand, in the field of black photospacers for liquid crystal display devices, Patent Document 3 discloses a negative photosensitive composition containing an acrylate compound having an adamantane skeleton and an epoxy acrylate resin having repeating units derived from biphenyltetracarboxylic dianhydride, and containing multiple types of organic pigments. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 181311 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-256850 [Patent Document 3] Japanese Patent Application Publication No. 2018-9194 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when a pixel division layer is formed using the negative-type photosensitive composition disclosed in Patent Document 1, the resulting organic EL display device has a problem of high driving voltage. Furthermore, when an economically advantageous low-concentration inorganic alkaline aqueous solution (e.g., 0.04 wt. % potassium hydroxide) is used as a developer instead of a high-concentration organic alkaline aqueous solution (e.g., 2.38 wt. % tetramethylammonium hydroxide), a pixel division layer cannot be formed due to insufficient alkali solubility of the film in the unexposed areas. On the other hand, the negative-type photosensitive composition disclosed in Patent Document 2 can form a pixel division layer by development using a low-concentration inorganic alkaline aqueous solution, but has a problem of high driving voltage, and when a black pigment is added to impart light-blocking properties, the driving voltage becomes even higher. The negative-type photosensitive composition disclosed in Patent Document 3 also has a problem of high driving voltage. [Means for solving the problem]

[0006] The present invention provides a negative photosensitive composition containing (a) one or more compounds selected from the group consisting of (meth)acrylate compounds having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, (meth)acrylate compounds having one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule, and salts thereof, and (b) a photopolymerization initiator.

[0007] [ka]

[0008] In formula (1), R 1 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents the bonding site with an oxygen atom. [Effects of the Invention]

[0009] The negative photosensitive composition of the present invention can be developed with a low-concentration inorganic alkaline aqueous solution, and can form a pixel dividing layer that achieves both a small taper angle and a low driving voltage for an organic EL display device. [Brief explanation of the drawings]

[0010] [Figure 1] 1 shows a manufacturing process of an organic EL display device including a step of forming a pixel dividing layer in all examples and comparative examples. [Figure 2] FIG. 10 is a cross-sectional view showing the taper angle θ of the pixel division layer in all examples and comparative examples. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. A numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. The pixel division layer refers to a pixel division layer provided in an organic EL display device. Visible light refers to light in the wavelength range of 380 nm or more and less than 780 nm, and near-ultraviolet light refers to light in the wavelength range of 200 nm or more and less than 380 nm. Light-shielding refers to the function of reducing the intensity of transmitted light compared to the intensity of light incident perpendicularly to the cured film, and light-shielding properties refer to the degree to which visible light is blocked. The photosensitive composition refers to a photosensitive composition that is photosensitive to near-ultraviolet light and is alkali-developable. The weight-average molecular weight (Mw) is a value obtained by analyzing by gel permeation chromatography using tetrahydrofuran as a carrier and converting it using a calibration curve based on standard polystyrene. The "CI" used to refer to some colorants is an abbreviation for Color Index Generic Name, which is based on the Color Index published by the Society of Dyers and Colorists. For colorants registered in the Color Index, the Color Index Generic Name indicates the chemical structure and crystalline form of the pigment or dye. Carbon blacks classified as CI Pigment Black 7, for example, are classified as inorganic black pigments. Total solids refers to the percentage (by weight) of components in a negative-working photosensitive composition, excluding solvents and water.

[0012] The present inventors have conducted extensive research into the structure of a photopolymerizable monomer component that contributes to reducing driving voltage while taking advantage of the excellent hydrophobicity, rigidity, and heat resistance of the fluorene skeleton and the adamantane skeleton, and have found that a (meth)acrylate compound with a specific structure has an extremely significant effect in solving the above-mentioned problems.

[0013] That is, the present invention provides a negative photosensitive composition containing (a) one or more compounds selected from the group consisting of (meth)acrylate compounds having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, (meth)acrylate compounds having one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule, and salts thereof, and (b) a photopolymerization initiator.

[0014] [ka]

[0015] In formula (1), R 1 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents the bonding site with an oxygen atom.

[0016] The negative photosensitive composition of the present invention contains the above-mentioned component (a), which has a characteristic structure and provides three effects.

[0017] The first effect is that a developed film having a low taper angle can be obtained by suppressing the occurrence of a hollowed-out cross-sectional shape, i.e., undercut, which can occur when the dissolution of the bottom of the film progresses excessively compared to the surface layer of the film in a development process using a low-concentration inorganic alkaline aqueous solution. As a second effect, the pixel division layer exhibits appropriate reflowability in the curing step described below, and can form a pixel division layer having an even lower taper angle than a developed film. As a third effect, an organic EL display device including the pixel division layer can be driven at a lower voltage.

[0018] Lowering the driving voltage reduces the burden on the light-emitting elements, extending their light-emitting lifespan, and also reduces power consumption, thereby improving the value of organic EL display devices.

[0019] The developer used in manufacturing a color filter consisting of a black matrix and a transparent pixel portion containing red, green, and blue colors is usually a low-concentration inorganic alkaline aqueous solution. When manufacturing an organic EL display device having a color filter and a pixel dividing layer, it is possible to standardize processes such as the type of developer, the developing device, and the waste liquid treatment device, which may be more economically advantageous.

[0020] The 9,9-bisarylfluorene skeleton possessed by the compound belonging to component (a) means a skeleton represented by formula (2).

[0021] [ka]

[0022] In formula (2), Z represents an aryl group having a substituent.

[0023] As the 9,9-bisarylfluorene skeleton, a skeleton consisting of two substituted phenyl groups and one fluorene skeleton is preferred from the viewpoint of lowering the driving voltage, that is, a 9,9-bisphenylfluorene skeleton is preferred.

[0024] The adamantane skeleton possessed by the compound belonging to component (a) means the skeleton represented by formula (37).

[0025] [ka]

[0026] A (meth)acrylate compound refers to a compound having a methacryloxy group and / or an acryloxy group. Therefore, compounds belonging to component (a) have a methacryloxy group and / or an acryloxy group. These functional groups function as radically polymerizable groups that crosslink with the radical active species generated from the photopolymerization initiator (b) during the exposure step described below. In other words, these functional groups are the source of negative photosensitivity, rendering the exposed film insoluble in the developer and removing the unexposed film to obtain a patterned developed film.

[0027] The total number of methacryloxy groups and / or acryloxy groups in one molecule of the compound belonging to component (a) is preferably 2 or more in order to suppress undercut due to overdevelopment of the film bottom. In order to obtain adequate reflowability in the curing step described below and form a pixel dividing layer with a low taper angle at the edge of the opening, the total number is preferably 4 or less, and more preferably 2 or less. That is, the negative-type photosensitive composition of the present invention more preferably contains one or more compounds selected from the group consisting of (a) a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule, one structure represented by formula (1) in the molecule, and a total of two methacryloxy groups and / or acryloxy groups, a (meth)acrylate compound having one or two adamantane skeletons in the molecule, one structure represented by formula (1) in the molecule, and a total of two methacryloxy groups and / or acryloxy groups, and a salt thereof.

[0028] From the viewpoint of reactivity when synthesizing a compound belonging to component (a), the structure represented by formula (1) is preferably a structure derived from a dicarboxylic acid anhydride.

[0029] Examples of dicarboxylic acid anhydrides include maleic anhydride (R 1 the number of carbon atoms in the compound (1) obtained after the reaction is 2), succinic anhydride (in the compound (1) obtained after the reaction, R 1 the number of carbon atoms in the compound (R 1the number of carbon atoms in the compound (1) obtained after the reaction is 5), 1,2,3,6-tetrahydrophthalic anhydride (in the compound (1) obtained after the reaction, R 1 the number of carbon atoms in the compound (1) obtained after the reaction is 6), 3,4,5,6-tetrahydrophthalic anhydride (in the compound (1) obtained after the reaction, R 1 the number of carbon atoms in the compound (1) obtained after the reaction is 6), 1,2-cyclohexanedicarboxylic acid anhydride (in the compound (1) obtained after the reaction, R 1 the number of carbon atoms in the compound (R 1 the number of carbon atoms in the compound (R 1 the number of carbon atoms in the compound (1) obtained after the reaction is: 6), 4-hydroxyphthalic anhydride (in the compound (1) obtained after the reaction, R 1 the number of carbon atoms in the compound (R 2 ), exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (the compound (R 2 ) in the compound (R 2 ) obtained after the reaction) 1 the number of carbon atoms in the compound (1) obtained after the reaction is: 6), 2,3-norbornene dicarboxylic acid anhydride (in the compound (1) obtained after the reaction, R 1 the carbon number of which is 7), cis-5-norbornene-2,3-dicarboxylic acid anhydride (in the formula (1) obtained after the reaction, R 1 the number of carbon atoms of which is 7), 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride (in the formula (1) obtained after the reaction, R 1 the number of carbon atoms of which is 7), 3-ethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride (in the formula (1) obtained after the reaction, R 1 the number of carbon atoms in the compound (R 1 The carbon number of the divalent hydrocarbon group R 1 The number of carbon atoms in R is preferably 2 to 6 from the viewpoint of reducing the driving voltage. 1 It is also possible to use a plurality of (meth)acrylate compounds having different structures.

[0030] At least a portion of component (a) may be present in the negative-working photosensitive composition in the form of a salt. Examples of salts include ammonium salts, amine salts, and metal salts. Ammonium salts are preferred from the viewpoint of reducing driving voltage, and specific examples include salts formed by ammonium cations at the carboxyl groups in the structure represented by formula (1) above. Specific examples of ammonium salts include tetramethylammonium salts, tetraethylammonium salts, tetra-n-propylammonium salts, tetraisopropylammonium salts, tetra-n-butylammonium salts, tetra-sec-butylammonium salts, tetra-tert-butylammonium salts, tetra-n-pentylammonium salts, tetra-n-hexylammonium salts, tetraheptylammonium salts, trimethylmonoethylammonium salts, triethylmonoethylammonium salts, tri-n-propylmonomethylammonium salts, tri-n-propylmonoethylammonium salts, trimethylmonophenylammonium salts, and trimethylmonobenzylammonium salts. These ammonium salts may be derived, for example, from tetraalkylammonium hydroxides or tetraalkylammonium halides.

[0031] (a) As the (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, a compound obtained by adding a dicarboxylic acid anhydride to one of two hydroxyl groups of a (meth)acrylate compound obtained by derivatizing a fluorene compound having a 9,9-bisphenylfluorene skeleton and two epoxy groups in the molecule with (meth)acrylic acid is preferred, and specifically, a compound represented by formula (3) is preferred.

[0032] That is, when the negative-type photosensitive composition of the present invention contains, as component (a), a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, it is preferable that component (a) contains a compound represented by formula (3) and / or a salt thereof in order to reduce the driving voltage.

[0033] [ka]

[0034] In formula (3), a and b are integers, each independently representing 0 or 1. R 2 and R 3 each independently represents an ethylene group or a propylene group. c and d are integers, each independently representing 0 to 3. R 4 and R 5 each independently represents a hydrogen atom or a methyl group. R 6 and R 7 In the formula (4), one of the R groups is a hydrogen atom and the other is a structure represented by formula (4). 8 and R 9 each independently represents an alkyl group having 1 to 3 carbon atoms. e and f are integers, each independently representing 0 to 2.

[0035] [ka]

[0036] In formula (4), R 10 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents the bonding site with an oxygen atom. In formula (3), it is preferable that all of the integers a, b, c, and d are 0 from the viewpoint of reducing the driving voltage. 4 and R 5 In order to obtain a low taper angle, a hydrogen atom is preferable for each of the integers c and d. When the integers c and d are 1 to 3, R 2 and R 3 Each of R is preferably an ethylene group. 8 and R 9 In both cases, a methyl group is preferred. 10 Specific examples of the formula (1) include R 1The carbon number is preferably 2 to 6 from the viewpoint of reducing the driving voltage, and it is more preferable that the compound has an alicyclic structure. Specific examples of salts are those described above, and are preferably ammonium salts.

[0037] When the negative-type photosensitive composition of the present invention contains, as component (a), a (meth)acrylate compound having one 9,9-bisarylfluorene skeleton in the molecule and one structure represented by formula (1) in the molecule, it is most preferable that component (a) contains a compound represented by formula (5) and / or a salt thereof, from the viewpoint of reducing the driving voltage.

[0038] [ka]

[0039] In formula (5), R 11 and R 12 each independently represents a hydrogen atom or a methyl group. R 13 and R 14 R represents a structure represented by formula (6), formula (7), or formula (8), one of which is a hydrogen atom and the other is a structure represented by formula (6), formula (7), or formula (8). 15 and R 16 represents a methyl group. g and h are integers, each independently representing 0 to 2.

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] In the formulas (6) to (8), * represents a bonding site with an oxygen atom. In the case of a salt, the same points as those described above can be applied to specific examples, and ammonium salts are preferred.

[0044] On the other hand, as the (meth)acrylate compound or a salt thereof having one or two adamantane skeletons and one structure represented by formula (1) in the molecule, a compound obtained by adding a dicarboxylic acid anhydride to one of two hydroxyl groups of a (meth)acrylate compound obtained by derivatizing an adamantane compound having one or two adamantane skeletons and two epoxy groups in the molecule with (meth)acrylic acid is preferred, and specifically, a compound having a structure represented by formula (38) or formula (39) or a salt thereof is preferred.

[0045] That is, when the negative-type photosensitive composition of the present invention contains, as component (a), a (meth)acrylate compound or a salt thereof having one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule, from the viewpoint of reducing the driving voltage, it is preferable that the (meth)acrylate compound having one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule has a structure represented by formula (38) or a structure represented by formula (39).

[0046] That is, in the negative-type photosensitive composition of the present invention, as component (a), it is more preferable that the (meth)acrylate compound having one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule has a structure represented by formula (38).

[0047] [ka]

[0048] In formula (38), n 1 is an integer and represents 1 or 2. 2 is an integer and represents 0 or 1. 22represents an alkyl group having 1 to 3 carbon atoms. * represents the bonding site with the carbon atom.

[0049] [ka]

[0050] In formula (39), n 3 and n 4 is an integer and represents 0 or 1. 23 and R 24 each independently represents an alkyl group having 1 to 3 carbon atoms. * represents the bonding site to the carbon atom.

[0051] As the compound having a structure represented by formula (38) or a salt thereof, it is preferable that the component (a) contains a compound represented by formula (40) and / or a salt thereof, from the viewpoint of reducing the driving voltage.

[0052] That is, the negative photosensitive composition of the present invention preferably contains, as component (a), a (meth)acrylate compound represented by formula (40) and / or a salt thereof.

[0053] [ka]

[0054] In formula (40), n 5 and n 6 are integers, each independently representing 0 or 1. R 25 and R 26 each independently represents an ethylene group or a propylene group. R 27 and R 28 In the formula (41), one of the two is a hydrogen atom and the other is a structure represented by formula (41). 7 is an integer and represents 1 or 2. 8 is an integer and represents 0 or 1. R 29 and R 30each independently represents a hydrogen atom or a methyl group. R 31 represents an alkyl group having 1 to 3 carbon atoms.

[0055] [ka]

[0056] In formula (41), R 32 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents the bonding site with an oxygen atom.

[0057] R 29 and R 30 In order to obtain a low taper angle, hydrogen atoms are preferred. 5 and n 6 When at least one of these is 1 or 2, from the viewpoint of reducing the driving voltage, R 25 and R 26 is preferably an ethylene group. 32 Specific examples of the formula (1) include R 1 The carbon number is preferably 2 to 6 from the viewpoint of reducing the driving voltage, and it is more preferable that the compound has an alicyclic structure. Specific examples of salts are those described above, and ammonium salts are preferred. The compounds belonging to component (a) above may be used alone or in combination.

[0058] The content of the component (a) is preferably 5 to 95% by weight of the total solid content in the negative photosensitive composition in order to achieve both a low taper angle and a low driving voltage. The component (a) contained in the negative photosensitive composition of the present invention is a material that can be measured by proton nuclear magnetic resonance spectroscopy (hereinafter referred to as " 1 The chemical structure can be identified by known analytical methods such as 1 H-NMR and LC-MS.

[0059] (a) A (meth)acrylate compound having one 9,9-bisarylfluorene skeleton and one structure represented by formula (1) in the molecule can be synthesized, for example, by the following two-step reaction.

[0060] In the first reaction step, a starting material, a fluorene compound having one 9,9-bisarylfluorene skeleton in the molecule and two epoxy groups in the molecule, is dissolved in a non-reactive solvent, and 2 moles of methacrylic acid and / or acrylic acid are added to 1 mole of the starting material in an inert gas atmosphere to cause a reaction, thereby obtaining a solution containing an epoxy (meth)acrylate compound having a 9,9-bisarylfluorene skeleton as an intermediate product.

[0061] Preferred examples of the fluorene compound having one 9,9-bisarylfluorene skeleton and two epoxy groups in the molecule as a starting material include 9,9-bis[4-(2-glycidyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-glycidyloxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-glycidyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-glycidyloxyethoxy)-3-ethylphenyl]fluorene (all manufactured by Osaka Gas Chemicals Co., Ltd.).

[0062] The amount of solvent used in the first reaction step is set so that the solids content in the reaction system is 10 to 70 wt%, preferably 20 to 60 wt%. To simultaneously suppress gelation and promote the reaction, the reaction conditions are as follows: a liquid temperature of 50 to 130°C, preferably 70 to 110°C, a heating time of 1 to 15 hours, preferably 2 to 10 hours, and stirring. By maintaining the liquid temperature at 130°C or below during heating, the reaction between fluorene compounds having one 9,9-bisarylfluorene skeleton and two epoxy groups in the molecule is suppressed, thereby suppressing the generation of by-products having two or more 9,9-bisarylfluorene skeletons in the molecule. Examples of suitable non-reactive solvents include propylene glycol monomethyl ether acetate, methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, toluene, and xylene.

[0063] Additionally, a thermal polymerization inhibitor such as hydroquinone or methoquinone may be used to suppress the self-polymerization of methacrylic acid and / or acrylic acid and the formation of dimers of intermediate products. The amount of the thermal polymerization inhibitor used is preferably 0.01 to 0.1 wt % based on the total amount of methacrylic acid and acrylic acid. The end point of the first reaction step can be determined by confirming the disappearance of methacrylic acid and / or acrylic acid in the reaction system using liquid chromatography mass spectrometry (hereinafter referred to as "LC-MS") or infrared spectroscopy (hereinafter referred to as "IR"). A simpler method is to consider the time when the acid value in the system falls below 1 mgKOH / g as the end point of the reaction. After the end point of the reaction is reached, the second reaction step is then carried out.

[0064] In the second reaction step, 1 mol of dicarboxylic anhydride is further added to 1 mol of the intermediate product to cause a dehydration reaction, thereby obtaining a solution containing a compound belonging to component (a). The above-mentioned group of compounds can be preferably used as the dicarboxylic anhydride. To obtain component (a) in high yield, it is desirable to add 0.3 to 0.5 mol of dicarboxylic anhydride to 1 mol of hydroxyl groups in the intermediate product and carry out the reaction. If necessary, the second reaction step may be carried out after isolating only the intermediate product from the solution containing the intermediate product obtained in the first reaction step and subjecting it to treatment such as purification.

[0065] The reaction conditions in the second reaction step are a liquid temperature of 50 to 100°C, preferably 60 to 90°C, and a heating time of 4 to 20 hours, preferably 8 to 15 hours, while stirring is maintained.

[0066] A catalyst may be used in the first and second reaction steps, if necessary. Examples of the catalyst include basic catalysts, such as tertiary amines (e.g., trimethylamine and triethylamine), and tetraalkylammonium halides (e.g., tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, and tetrabutylammonium chloride). Tetraalkylammonium halides are preferred because they function as phase transfer catalysts and can improve the yield of component (a). The reaction endpoint of the second reaction step can be determined by the disappearance of the intermediate product by LC-MS.

[0067] Furthermore, by performing an isolation procedure using silica gel chromatography to remove any remaining unreacted starting materials, catalysts, and / or by-products, and then performing a drying treatment under reduced pressure, a compound belonging to component (a) can be obtained in high purity.

[0068] Alternatively, at least a portion of component (a) may be converted into an ammonium salt by adding a tetraalkylammonium halide or the like to a solution containing the compound belonging to component (a) obtained to form a salt with the carboxyl group, followed by reprecipitation and washing with water to remove the halogen anions and purify the solution.Instead of the tetraalkylammonium halide described above, potassium hydroxide, sodium hydroxide, or the like may be used to convert at least a portion of component (a) into an alkali metal salt such as a potassium salt or a sodium salt.

[0069] Based on the above method, by synthesizing the compounds by changing the type of starting material and / or dicarboxylic acid anhydride, it is possible to easily synthesize various (meth)acrylate compounds having one 9,9-bisarylfluorene skeleton with different structures in the molecule and one structure represented by formula (1) in the molecule.

[0070] On the other hand, a (meth)acrylate compound having one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule can be synthesized by a similar method including the first and second reaction steps described above, using, for example, a compound having one or two adamantyl groups in the molecule and two or three epoxy groups as a starting material instead of the fluorene compound having one 9,9-bisarylfluorene skeleton in the molecule and two epoxy groups in the molecule.

[0071] Preferred examples of the starting compound having one or two adamantyl groups and two or three epoxy groups in the molecule include compounds represented by formula (42), (43), (44), (45), (46), (47), and (48). Commercially available products of these compounds include the "Adamantate (registered trademark)" XE series (manufactured by Idemitsu Kosan Co., Ltd.).

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] Preferred specific examples of the (meth)acrylate compound having one 9,9-bisarylfluorene skeleton and one structure represented by formula (1) in the molecule include a compound represented by formula (49) and a compound represented by formula (50).

[0080] [ka]

[0081] [ka]

[0082] Preferred specific examples of the (meth)acrylate compound having one or two adamantane skeletons in the molecule and one structure represented by formula (1) in the molecule include a compound represented by formula (51) and a compound represented by formula (52).

[0083] [ka]

[0084] [ka]

[0085] In this specification, a (meth)acrylate compound or a salt thereof having one 9,9-bisarylfluorene skeleton, one or two adamantane skeletons, and one structure represented by formula (1) in the molecule is defined as belonging to the (meth)acrylate compound having one 9,9-bisarylfluorene skeleton and one structure represented by formula (1) in the molecule. An example of a compound falling under this category is a compound represented by formula (53).

[0086] [ka]

[0087] The negative-type photosensitive composition of the present invention contains (b) a photopolymerization initiator. Component (b) is not particularly limited as long as it generates a radical active species upon irradiation with actinic rays and has the effect of initiating a photoradical polymerization reaction of the (meth)acrylate compound containing component (a).

[0088] Examples of component (b) include oxime ester-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators. Of these, oxime ester-based photopolymerization initiators, which are highly sensitive to near-ultraviolet light, are preferred in order to achieve both a low taper angle and a low driving voltage. Sensitivity may be adjusted by using an oxime ester-based photopolymerization initiator in combination with a non-oxime ester-based photopolymerization initiator in order to adjust the difference between the dimensions of the light-shielding portion of the exposure mask and the dimensions of the openings in the pixel dividing layer, i.e., the mask bias in the exposure step, to a desired range.

[0089] Examples of oxime ester photopolymerization initiators include "ADEKA CRUISE (registered trademark)" NCI-831E (manufactured by ADEKA CORPORATION, hereinafter referred to as "NCI-831E"), compounds described in JP 2008 / 100955 A, compounds described in WO 2006 / 018405 A, "Irgacure (registered trademark)" OXE01 (hereinafter referred to as "OXE01"), OXE02, OXE03, and OXE04 (all manufactured by BASF). NCI-831E is a compound with the same structure as NCI-831 described in Patent Document 1.

[0090] The content of the (b) photopolymerization initiator is preferably 5 to 95% by weight of the total solid content in the negative photosensitive composition in order to achieve both a small taper angle and a low driving voltage.

[0091] The negative photosensitive composition of the present invention preferably further contains a colorant. By including a colorant, it is possible to impart light-blocking properties to the pixel division layer. Known pigments and dyes can be used as the colorant, and from the viewpoints of uniformity of the light-blocking properties of the pixel division layer within the substrate surface and low driving voltage, a pigment (c) is preferred. That is, the negative photosensitive composition of the present invention preferably further contains a pigment (c). The pigment referred to here does not include metal particles such as silver particles and copper particles.

[0092] (c) Pigments include organic pigments and inorganic pigments, with organic pigments being preferred due to their high insulating properties and low dielectric constants, such as organic black pigments, organic yellow pigments, organic orange pigments, organic red pigments, organic blue pigments, and organic purple pigments.

[0093] Examples of organic black pigments include lactam-based organic black pigments, perylene-based organic black pigments, and azomethine-based organic black pigments. Examples of organic yellow pigments include CI Pigment Yellow 120, 138, 139, 151, 175, 180, 185, 181, 192, 193, and 194. Examples of organic orange pigments include CI Pigment Orange 13, 36, 43, 60, 61, 62, 64, 71, and 72. Examples of organic red pigments include CI Pigment Red 122, 123, 149, 178, 177, 179, 180, 189, 190, 202, 209, 254, 255, and 264. Examples of organic blue pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:6, 16, 25, 56, 57, 60, 61, 64, 65, 66, 75, 79, and 80. Examples of organic purple pigments include CI Pigment Violet 19, 23, 29, 32, and 37.

[0094] Examples of inorganic black pigments include carbon black, titanium nitride, titanium oxynitride, zirconium nitride, and zirconium oxynitride. When an inorganic black pigment is contained, carbon black is preferred, and examples of commercially available products include "EMPEROR (registered trademark)" 1200, 1600, and 1800, "MONARCH (registered trademark)" 700, 800, 1000, and 1300, and TPK1227.

[0095] In particular, from the viewpoint of reducing the driving voltage, the negative photosensitive composition of the present invention preferably contains a lactam-based organic black pigment as the pigment (c), and more preferably contains an organic red pigment having an anthraquinone skeleton and / or an organic blue pigment having an anthraquinone skeleton in addition to the lactam-based organic black pigment.

[0096] The lactam-based organic black pigment referred to here refers to an organic black pigment containing a compound having two lactam skeletons in the molecule. An example of the lactam-based organic black pigment is bis-oxodihydroindolylene-benzodifuranone, as described in International Publication No. 2009 / 010521. Among these, lactam-based organic black pigments containing a compound represented by formula (9) are preferred from the viewpoint of low-voltage operation.

[0097] [ka]

[0098] The lactam-based organic black pigment containing the compound represented by formula (9) may be a commercially available product, and examples thereof include "Irgaphor (registered trademark)" Black S0100CF and Experimental Black 582 (both manufactured by BASF). An example of an organic red pigment having an anthraquinone skeleton is CI Pigment Red 177, and an example of an organic blue pigment having an anthraquinone skeleton is CI Pigment Blue 60.

[0099] The average primary particle size of the organic pigment is preferably 10 to 150 nm, more preferably 40 to 100 nm. The average primary particle size here refers to the number-average value of primary particle sizes calculated by a particle size measurement method using an image analysis particle size distribution analyzer. Methods for obtaining finely divided organic pigment powder include the acid paste method, in which a solution of a pigment crude dissolved in concentrated sulfuric acid is mixed with a large amount of water to precipitate and granulate, and the solvent salt milling method, in which an organic pigment, a water-soluble inorganic salt, and a water-soluble organic solvent are kneaded under heating and wet-pulverized while adjusting the particle shape through crystal growth.

[0100] The content of the (c) pigment is preferably 10 to 40% by weight, more preferably 15 to 30% by weight, of the total solid content of the negative photosensitive composition, from the viewpoint of achieving both light-shielding properties and a low driving voltage.

[0101] When the negative-working photosensitive composition of the present invention contains the pigment (c), it preferably further contains a pigment dispersant (d). The inclusion of the pigment dispersant (d) makes it easier to control the particle size distribution of all particle components, including the pigment (c), within a desired range described below, and also has the effect of stabilizing the dispersion state of the pigment (c) in the negative-working photosensitive composition.

[0102] (d) Pigment dispersants include polymeric dispersants and non-polymeric dispersants, and these may be used in combination.

[0103] A polymeric dispersant refers to a compound having a weight-average molecular weight (Mw) of 1,000 or more, which contains a polymer chain consisting of repeating units derived from a monomer and at least one highly polar functional group selected from the group consisting of a tertiary amino group, a quaternary ammonium salt group, a phosphate group, and a sulfo group. (c) In order to achieve both pigment dispersion stabilization and low driving voltage, a tertiary amino group or a phosphate group is preferred as the highly polar functional group. Examples of polymer chains include polyether polymer chains, (meth)acrylic polymer chains, polyurethane polymer chains, polyester polymer chains, and polyamide polymer chains. Among these, polyether polymer chains or (meth)acrylic polymer chains are preferred from the viewpoint of low driving voltage.

[0104] Preferred examples of polymeric dispersants having a polyether polymer chain and a tertiary amino group include dispersants made of a tertiary polyamine in which a linear polyether polymer chain is grafted onto an aliphatic primary amine. Preferred examples of polymeric dispersants having a (meth)acrylic polymer chain and a tertiary amino group include dispersants made of an AB block copolymer or a BAB block copolymer, each of which has an A block with a tertiary amino group in its side chain and a B block with no tertiary amino group in its side chain. Preferred examples of the A block include polymeric chains containing structural units derived from N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate. Preferred examples of polymeric dispersants having a (meth)acrylic polymer chain and a phosphate group include random copolymers of structural units derived from a (meth)acrylate compound with a phosphate group and a (meth)acrylate compound without a phosphate group. Examples of the (meth)acrylate compound having a phosphate group include 2-methacryloyloxyethyl acid phosphate, acid phosphoxyethyl (meth)acrylate, acid phosphoxypropyl (meth)acrylate, and acid phosphoxypolyoxypropylene glycol (meth)acrylate. The polymer-type dispersant may be added during the production of the pigment dispersion liquid described below, or during the production of the negative photosensitive composition.

[0105] The non-polymeric dispersant refers to a compound that has at least one highly polar functional group selected from the group consisting of a tertiary amino group, a quaternary ammonium base, a phosphate group, and a sulfo group, and does not belong to the aforementioned polymeric dispersants.

[0106] Examples of non-polymeric dispersants include organic dye derivatives (synergists) obtained by derivatizing pigments or dyes, as well as triazine derivatives. Triazine derivatives are preferred from the viewpoint of low driving voltage. Compounds having an organic dye residue and a triazine ring are defined as belonging to the triazine derivatives. Non-polymeric dispersants may be added as a micronization promoter when obtaining the above-mentioned micronized organic pigment powder, or may be added during the production of the pigment dispersion liquid described below.

[0107] The type of organic dye residue is not particularly limited, but examples of organic dye derivatives include compounds represented by formula (10) and compounds represented by formula (11).

[0108] [ka]

[0109] [ka]

[0110] From the viewpoint of reducing the driving voltage, the triazine derivative is preferably a compound having a 1,3,5-triazine ring and a sulfo group or an N,N-dialkylamino group, and a compound having a structure represented by formula (12) is preferred. That is, the negative photosensitive composition of the present invention preferably further contains (d) a pigment dispersant, and the pigment dispersant preferably contains a compound having a structure represented by formula (12). The compound having a structure represented by formula (12) may be particularly effective as a technical means for adjusting the value of XY to a desired range, as described below.

[0111] [ka]

[0112] In formula (12), R 17 represents a divalent hydrocarbon group. 18 represents a sulfo group or an N,N-dialkylamino group. * represents a bonding site.

[0113] From the viewpoint of lowering the driving voltage, R 18 is a sulfo group, R 17 is preferably a phenylene group. 18 is an N,N-dialkylamino group, R 17 is preferably an alkylene group having 1 to 5 carbon atoms.

[0114] Examples of the compound having the structure represented by formula (12) include a compound having the structure represented by formula (13) and a compound having the structure represented by formula (14).

[0115] [ka]

[0116] In formula (13), * represents a binding site.

[0117] [ka]

[0118] In formula (14), R 19 represents an alkylene group having 1 to 5 carbon atoms. 20 and R 21 are the same and represent an alkyl group having 1 to 5 carbon atoms. * represents a bonding site.

[0119] As specific examples of the compound having a structure represented by formula (13) and the compound having a structure represented by formula (14), a compound represented by formula (15) and a compound represented by formula (16) are shown below, but the compound having a structure represented by formula (12) is not limited to anthraquinone-based triazine derivatives.

[0120] [ka]

[0121] [ka]

[0122] The negative photosensitive composition of the present invention may contain (e) an alkali-soluble resin.

[0123] The alkali-soluble resin refers to a polymer having hydroxyl and / or carboxyl groups as alkali-soluble groups, a weight-average molecular weight (Mw) of 1,000 to 150,000, and a compound that does not belong to the above-mentioned components (a) to (d) or the below-mentioned component (f). The inclusion of the alkali-soluble resin makes it easier to control the dissolution rate of the unexposed portion of the film in a developer.

[0124] (e) Examples of alkali-soluble resins include alkali-soluble (meth)acrylic resins, alkali-soluble epoxy (meth)acrylate resins, alkali-soluble polyimide resins, alkali-soluble polyimide precursors, and alkali-soluble polysiloxane resins.

[0125] The negative photosensitive composition of the present invention may contain, as component (f), a (meth)acrylate compound other than component (a). When component (a) contains a compound represented by formula (3) or a compound represented by formula (5), the negative photosensitive composition of the present invention preferably further contains a tetrafunctional or higher functional (meth)acrylate compound from the viewpoint of reducing the driving voltage.

[0126] Examples of the tetrafunctional (meth)acrylate compound include a compound represented by formula (17) and a compound represented by formula (18).

[0127] [ka]

[0128] [ka]

[0129] An example of a pentafunctional (meth)acrylate compound is dipentaerythritol penta(meth)acrylate. Examples of a hexafunctional (meth)acrylate compound include dipentaerythritol hexaacrylate and ε-caprolactone-modified hexafunctional acrylates "KAYARAD (registered trademark)" DPCA-20, DPCA-30, DPCA-60 (hereinafter referred to as "DPCA-60") and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.). Furthermore, an example of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is "KAYARAD (registered trademark)" DPHA.

[0130] From the viewpoint of lowering the driving voltage, the negative photosensitive composition of the present invention preferably further contains (g) a compound represented by formula (54). The content of component (g) is preferably 0.01 to 0.5% by weight based on 100% by weight of the solid content of the negative photosensitive composition.

[0131] [ka]

[0132] In formula (54), n 9 ~n 11 are integers, each independently representing 0 to 2. R 33 ~R 35 each independently represents a methyl group, an ethyl group, a methoxy group, or an ethoxy group.

[0133] Specific examples of the component (g) include triphenylphosphine, tris(3,5-dimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(m-methoxyphenyl)phosphine, and tris(o-methoxyphenyl)phosphine.

[0134] The negative photosensitive composition of the present invention may further contain a solvent. By containing a solvent, the viscosity, thixotropy, etc. of the negative photosensitive composition can be adjusted, and the coatability can be improved.

[0135] As the solvent, from the viewpoint of dissolving power and dispersion stability, it is preferable to use ether-based solvents and acetate-based solvents either alone or in combination.

[0136] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0137] Examples of acetate-based solvents include propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 3-methoxybutyl acetate (hereinafter referred to as "MBA"), butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.

[0138] The water content in the negative photosensitive composition of the present invention is preferably 1% by weight or less, more preferably 0.5% by weight or less, from the viewpoint of lowering the driving voltage.

[0139] The negative photosensitive composition of the present invention may further contain other components such as a thermal crosslinking agent, a surfactant, a leveling agent, an antioxidant, and an ultraviolet absorber.

[0140] The negative photosensitive composition of the present invention can be prepared by mixing and stirring components (a) and (b). When components (c) to (g) are further included, the composition may be prepared, for example, by mixing components (c), (d), and (e) with a solvent to prepare a pigment dispersion by wet dispersion treatment, and then mixing and stirring components (a), (b), (f), and (g), the solvent, and other components with the pigment dispersion, and optionally filtering the mixture.

[0141] The disperser used for wet dispersion treatment may be either a wet media disperser or a wet medialess disperser, but the use of a wet media disperser is preferable due to its superior dispersion treatment speed and economical advantages. Examples of wet media dispersers include bead mills such as "Levomill (registered trademark)" (manufactured by Asada Iron Works), "Nano Getter (registered trademark)" (manufactured by Ashizawa Finetech), "DYNO-MILL (registered trademark)" (manufactured by Willy A. Bachofen), "Spike Mill (registered trademark)" (manufactured by Inoue Manufacturing Co., Ltd.), "Sand Grinder (registered trademark)" (manufactured by DuPont), "Ultra Apex Mill Advance (registered trademark)" (manufactured by Hiroshima Metal & Machinery Co., Ltd.), and "NEO-Alpha Mill (registered trademark)" (manufactured by AIMEX Co., Ltd.).

[0142] Examples of media used in wet media dispersion treatment include zirconia beads and zircon beads. The diameter of the media is preferably 0.03 to 0.5 mmφ, and the higher the sphericity, the better. Specific examples of commercially available products include "Treceram (registered trademark)" (manufactured by Toray Industries, Inc.) and "YTZ (registered trademark)" (manufactured by Nikkato Corporation).

[0143] In the negative photosensitive composition of the present invention, the particle size distribution of all particle components including (c) pigment preferably satisfies the following relationship from the viewpoint of reducing the driving voltage. That is, in the particle size distribution of all particle components contained in the negative photosensitive composition measured by the dynamic light scattering method, the cumulative 50% particle diameter X (nm) based on the light scattering intensity and the cumulative 50% particle diameter Y (nm) based on the volume preferably satisfy the relationship of 10 nm < X - Y < 30 nm. More preferably, they satisfy the relationship of 10 nm < X - Y < 20 nm.

[0144] The cumulative 50% particle diameter X (nm) based on the light scattering intensity and the cumulative 50% particle diameter Y (nm) based on the volume are indicators shown based on two different criteria for one sample, and both values can be measured using the particle size distribution measuring device "SZ-100 (manufactured by Horiba, Ltd.)" of the dynamic light scattering method. The light source of the measuring device is a wavelength of 532 nm / 10 mW (semiconductor-excited solid-state laser), and the sample is not irradiated with near-ultraviolet light during measurement. The cumulative 50% means the particle diameter corresponding to 50% when accumulated from the small particle diameter side (0%) as the starting point in the cumulative particle size distribution curve to the large particle diameter side. The sample for measuring X and Y is prepared by mixing an equal amount of diluting solvent into the negative photosensitive composition in three portions so that the weight ratio of the negative photosensitive composition / diluting solvent is 1 / 99, and stirring on a shaker for 10 minutes. As the diluting solvent, the same solvent as the solvent contained in the negative photosensitive composition is used. As the value of the solvent viscosity required for measurement, the viscosity value of the diluting solvent used for dilution at 25 ° C (under atmospheric pressure) is input.

[0145] The cured film of the present invention is a cured film containing a cured product of a negative photosensitive composition.

[0146] The cured film of the present invention can be used, for example, for the pixel division layer or the TFT planarization layer of an organic EL display device, the black matrix or the black column spacer of a liquid crystal display device, the near-infrared highly transmissive black film of a solid-state imaging device, the near-infrared highly transmissive black film for the bezel of a touch panel, etc., and the application is not particularly limited.

[0147] The cured product refers to a cured product obtained through a process including at least a curing step in which a negative photosensitive composition is heated at a temperature of 200°C to 400°C under atmospheric pressure for 10 minutes or longer. The cured film can be obtained by a formation method including at least a coating step and a curing step. A simple method includes, for example, applying the negative photosensitive composition of the present invention to a substrate surface using a spin coater as a coating device, followed by heating at 230°C under atmospheric pressure for 30 minutes using a hot air oven as a heating device to obtain a solid cured film.

[0148] The method for producing the cured film of the present invention is more preferably a method for producing a cured film comprising: a coating step of applying a negative photosensitive composition to obtain a coated film; an exposure step of exposing the composition to actinic radiation in a pattern to obtain an exposed film having exposed and unexposed areas within its surface; a development step of developing the composition with an alkaline developer containing potassium hydroxide to obtain a developed film; and a curing step of thermally curing the composition by heating to obtain a cured film.

[0149] As the coating device used in the coating step, a spin coater or slit coater is preferably used because of its excellent thin film coating properties. After coating, pin gap pre-baking or contact pre-baking may be performed. The pre-baking temperature is preferably 50 to 150°C, and the pre-baking time is preferably 30 seconds to 5 minutes.

[0150] Examples of exposure devices used in the exposure process include steppers, mirror projection mask aligners (MPA), and parallel light mask aligners (PLA). The active actinic rays used during exposure are preferably the j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), or g-line (wavelength 436 nm) from a mercury lamp, with mixed rays containing at least the i-line being more preferred. Examples of negative exposure masks include masks in which a thin, opaque metal film such as chromium is patterned on one side of a substrate that is translucent at the exposure wavelength, such as glass, quartz, or film. By allowing only the openings to transmit the active actinic rays for pattern exposure, an exposed film having exposed and unexposed areas within the surface can be obtained. Here, the exposed area refers to the exposed area, and the unexposed area refers to the unexposed area.

[0151] In the development step, unexposed areas are removed by development to obtain a patterned developed film. Examples of development methods include showering, dipping, and puddling, in which the exposed film is immersed for 10 seconds to 3 minutes. The puddling method is preferred from the viewpoint of in-plane uniformity of the aperture width. As mentioned above, a low-concentration inorganic alkaline aqueous solution is preferred from an economical perspective. In this specification, a low-concentration alkaline aqueous solution refers to an alkaline aqueous solution with a concentration of 1% by weight or less. On the other hand, a high-concentration alkaline aqueous solution refers to an alkaline aqueous solution with a concentration exceeding 1% by weight. Examples of alkaline components include tetramethylammonium hydroxide and potassium hydroxide, and a 0.01 to 1% by weight potassium hydroxide aqueous solution is preferred from an economical perspective. An example of a commercially available high-concentration developer concentrate is "CD-150CR (registered trademark)" (manufactured by JSR Corporation), which contains potassium hydroxide and a surfactant. This can be diluted with deionized water to a potassium hydroxide concentration of preferably 0.01 to 1% by weight, more preferably 0.03 to 0.1% by weight. After the development step, a washing treatment using a shower of deionized water and / or a water removal treatment using an air jet may be added.

[0152] In the curing step, the developed film is thermally cured by heating, and at the same time, moisture and the like are evaporated to obtain a cured film. Examples of heating devices include a hot air oven and an IR oven. The heating temperature is preferably 200 to 300°C under atmospheric pressure, more preferably 220 to 260°C.

[0153] When the cured film of the present invention is used as a pixel dividing layer, the optical density (OD) per 1.0 μm of film thickness is preferably 0.5 or more, more preferably 0.7 or more, in order to suppress external light reflection and enhance the value of the display device. From the viewpoint of lowering the driving voltage, it is preferably 1.5 or less, more preferably 1.3 or less.

[0154] The optical density per 1.0 μm of film thickness refers to the value obtained by measuring the incident light intensity and transmitted light intensity of a cured film formed on a transparent substrate to a film thickness of 1.5 μm using an optical densitometer (X-Rite Corporation; X-Rite 361T), calculating the value using the following formula, and dividing the calculated value by 1.5, which is the film thickness value. A higher optical density indicates a higher light-blocking property. As the transparent substrate, a transparent glass substrate, Tempax (manufactured by AGC Technoglass Co., Ltd.), can be preferably used. Optical density = log 10 (I0 / I) I0: Incident light intensity I: transmitted light intensity.

[0155] The pixel division layer is typically formed to a thickness of 1 to 3 μm, and the taper angle at the edge of the opening of the developed film obtained after the development process is preferably 90° or less to improve the in-plane uniformity of the opening width after the curing process. The taper angle at the edge of the opening of the pixel division layer obtained after the curing process is preferably 50° or less, more preferably 40° or less, and even more preferably 35° or less to prevent pixels from not lighting up. To prevent a decrease in the light-blocking properties of the edge, the taper angle is preferably 10° or more, more preferably 15° or more, and even more preferably 20° or more. Furthermore, because light-emitting pixels are formed in the openings of the pixel division layer, it is desirable for the pixel division layer to be patterned into a partition wall shape so as to cover at least a portion of the surface of an electrode such as ITO (indium tin oxide).

[0156] The organic EL display device of the present invention is an organic EL display device comprising the cured film of the present invention, and has the technical feature of being able to obtain high luminance at a low driving voltage. [Example]

[0157] The present invention will be described in detail below with reference to examples and comparative examples, but the aspects of the present invention are not limited to these. First, the evaluation methods used in the examples and comparative examples will be described.

[0158] <Calculating the optimal exposure> An ITO film was formed on the entire surface of a 150 mm x 150 mm alkali-free glass substrate by sputtering, followed by annealing at 200°C for 30 minutes in a dry nitrogen atmosphere to obtain a substrate with a 10 nm thick ITO film. The negative photosensitive composition of the example or comparative example was applied to the surface of the ITO film using a spin coater, adjusting the rotation speed to obtain a final cured film thickness of 1.5 μm, to obtain a coating film. The coating film was prebaked at 100°C for 2 minutes under atmospheric pressure using a hot plate (SCW-636; Dainippon Screen Mfg. Co., Ltd.) to obtain a prebaked film-formed substrate. A double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; Union Optical Co., Ltd.) was used to perform pattern exposure using a sensitivity measurement grayscale mask (MDRM MODEL 4000-5-FS; Opto-Line International) with a mixed g, h, and i rays from an ultra-high pressure mercury lamp to obtain an exposed film. The film was then developed using a small photolithography developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) and a 0.04 wt% aqueous potassium hydroxide solution prepared by diluting CD-150CR with deionized water, using a puddle method. The puddle method refers to a method in which the developer is shower-applied to the surface of the exposed film for 10 seconds, and then the substrate is left to stand for the specified development time. The development time was calculated by multiplying the time it takes for the unexposed film to be dissolved and removed in the film depth direction by 1.5. The substrate was then rinsed with deionized water for 30 seconds using a shower method, and then dried by idling at 200 rpm for 30 seconds, yielding a developed film-formed substrate with a patterned developed film. Next, the developed film was observed using an FPD inspection microscope (MX-61L; Olympus Corporation), and the exposure dose (mJ / cm) was calculated when a negative exposure mask (light-shielding portion 40.0 μm, transparent portion 40.0 μm) with a line and space of 1:1 was opened so that the mask bias was -2.0 μm (opening width 38.0 μm, width of the developed film 42.0 μm). 2 The optimum exposure amount (exposure sensitivity) of the negative photosensitive composition was determined as follows: i-line equivalent value.

[0159] (1) Evaluation of the optical density (OD / μm) of the cured film For the optical density evaluation substrates formed with a 1.5 μm-thick cured film obtained in Examples 1 to 15 and Comparative Examples 1 to 5 and 7 to 11, the total optical density (Total OD value) was measured at three locations on the film surface using an optical densitometer (X-Rite 361T, manufactured by X-Rite Corporation) to calculate the average value. This value was then divided by 1.5, and the resulting value was rounded to one decimal place to represent the OD value per 1.0 μm of cured film thickness (OD / μm). Evaluation was based on the criterion that the higher the OD / μm, the better the light-blocking ability of the cured film. The OD value of Tempax without a cured film was separately measured and found to be 0.00, so the OD value of the optical density evaluation substrate was considered to be the OD value of the cured film. The thickness of the cured film was measured at three locations on the surface using a stylus film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom), and the average value was rounded off to one decimal place to obtain a value up to one decimal place.

[0160] (2) Calculating the XY values For the negative photosensitive compositions of Examples 1 to 15 and Comparative Examples 1 to 11, the particle size distribution was measured by the following method, and the values ​​of XY were calculated.

[0161] <How to prepare samples for particle size distribution measurement> The dilution solvent was mixed in equal amounts in three batches so that the weight ratio of the negative photosensitive composition to the dilution solvent was 1 / 99, and the mixture was stirred on a shaker for 10 minutes. The dilution solvent used was the same as the solvent contained in the negative photosensitive composition.

[0162] <Measurement conditions> Measurement equipment: Dynamic light scattering particle size distribution measurement equipment "SZ-100 (manufactured by Horiba Ltd.)" Light source: Wavelength 532nm / 10mW (semiconductor pumped solid state laser) Measurement sample liquid temperature: 25±1℃ (atmospheric pressure) Data analysis mode: Monodispersion mode (particle size distribution analyzer "SZ-100") Calculation method: The cumulative 50% particle diameter based on light scattering intensity was measured three times, and the average value was calculated and rounded to the nearest whole number to obtain the "cumulative 50% particle diameter X (nm) based on light scattering intensity." The cumulative 50% particle diameter based on volume was measured three times, and the average value was calculated and rounded to the nearest whole number to obtain the "cumulative 50% particle diameter Y (nm) based on volume." Furthermore, the value Y was subtracted from X to obtain the calculated value.

[0163] (3) Evaluation of the taper angle of the pixel division layer The pixel division layer-forming substrates obtained in Examples 1 to 15 and Comparative Examples 1 to 5 and 7 to 11 were fractured, and the pattern cross sections were observed at 15,000x magnification using a field emission scanning electron microscope "S-4800" (manufactured by Hitachi High-Technologies Corporation), and the taper angle θ of the pixel division layer was measured ( FIG. 2 ). The lower the taper angle, the better the results. Evaluation was based on the following criteria, with A to C being passed and D to E being rejected. Meanwhile, the developed films obtained in Examples 1 to 15 and Comparative Examples 1 to 5 and 7 to 11 before the curing step were also observed using the same method. If the taper angle of the pattern cross section of the developed film exceeded 90°, the developed film was evaluated as F and rejected, regardless of the taper angle of the pixel division layer. Note that in all Examples and Comparative Examples, no pixel division layer taper angles below 20° were observed. A: The taper angle of the pixel division layer is less than 35°. B: The taper angle of the pixel dividing layer is 35° or more and less than 40°. C: The taper angle of the pixel dividing layer is 40° or more and less than 50°. D: The taper angle of the pixel dividing layer is 50° or more and less than 80°. E: The taper angle of the pixel dividing layer is 80° or more. F: The taper angle of the developed film exceeds 90°.

[0164] (4) Evaluation of driving voltage of organic EL display devices The organic EL display devices obtained in Examples 1 to 15 and Comparative Examples 1 to 5 and 7 to 11 were allowed to emit light while changing the driving voltage from a lower limit of 2.0 V to an upper limit of 8.0 V. All of the organic EL display devices used for evaluation were bottom-emission type light-emitting devices in which emitted light is extracted from the substrate side. The luminance of the green light emitted from 220 light-emitting pixels was measured using a spectroradiometer (Konica Minolta CS-1000A) and converted to a value per unit area, resulting in a value of 6000 (cd / m 2 The driving voltage required to obtain a luminance of 1000 kJ / s was measured.

[0165] Note that "per unit area" here refers to the unit area of ​​the light-emitting pixel portion, and does not include the area of ​​the pixel dividing layer formation portion in the above conversion. The drive voltage was calculated by rounding off to one decimal place. The lower the drive voltage, the better the performance. Evaluation was based on the following criteria, with AA and A to C being considered pass, and D to E being considered fail. Note that if one or more unlit pixels occurred, it would be difficult to give a fair evaluation, so the result was considered fail, with an F being given. AA: The driving voltage is less than 4.0V. A: The driving voltage is 4.0V or more and less than 4.5V. B: The driving voltage is 4.5V or more and less than 5.0V. C: The driving voltage is 5.0V or more and less than 5.5V. D: The driving voltage is 5.5V or more and less than 6.0V. E: The driving voltage is 6.0 V or more. F: One or more unlit pixels occurred.

[0166] The following shows information on the chemical structures, solid contents, etc. of the various raw materials used in the examples and comparative examples. 1Analysis by H-NMR and LC-MS confirmed that none of the following ZCR-1569H, ZCR-1642H, binder resin-3, SPC-3410, alkali-soluble acrylic resin solution C, alkali-soluble polyimide resin B, polymer dispersant A, polymer dispersant solution B, fluorene acrylate solution I, fluorene acrylate solution J, fluorene acrylate solution K, fluorene acrylate solution L, fluorene acrylate solution M, and adamantane acrylate solution 4 contain component (a).

[0167] "S0100": "Irgaphor (registered trademark)" Black S0100CF. Corresponds to a lactam-based organic black pigment containing a compound represented by formula (9).

[0168] "Non-polymer dispersant 1": A compound represented by formula (10). An anthraquinone-based sulfonic acid derivative. Does not correspond to a compound having a structure represented by formula (12).

[0169] "Non-polymer dispersant 2": a compound represented by formula (15). An anthraquinone-based triazine derivative having a sulfo group. Corresponds to a compound having a structure represented by formula (12).

[0170] "Non-polymer dispersant 3": A compound represented by formula (16). An anthraquinone-based triazine derivative having an N,N-dialkylamino group. Corresponds to a compound having a structure represented by formula (12).

[0171] "Polymer-type dispersant A": Pigment dispersant 1 (solid content 100% by weight) disclosed in Synthesis Example 2 of JP 2020 / 70352 A. This is a polymer-type dispersant having a linear polyalkyleneamine structure and a polyether-based polymer chain.

[0172] "ZCR-1569H": PGMEA solution of alkali-soluble epoxy acrylate resin having a biphenyl skeleton in the main chain (manufactured by Nippon Kayaku Co., Ltd.: acid value of solids excluding solvent: 98 mg KOH / g, weight average molecular weight: 3900, solids content: 70 wt%).

[0173] "Binder Resin-3": A resin solution (acid value of solids excluding solvent: 110 mgKOH / g, weight-average molecular weight: 4000, methoxybutyl acetate solution with a solids content of 50% by weight) synthesized using the same synthesis method as disclosed in Synthesis Example 1 (synthesis of binder resin-3) of Patent Document 3. This is an alkali-soluble epoxy acrylate resin having repeating units derived from an acrylate compound having an adamantane skeleton and biphenyltetracarboxylic dianhydride.

[0174] "SPC-3410": PGMEA solution of alkali-soluble (meth)acrylic resin (manufactured by Showa Denko K.K.: solid content 42 wt%, weight average molecular weight (Mw) 7300, acid value of solids excluding solvent 75 mgKOH / g) having a structure in which the hydroxyl groups of a copolymer consisting of structural unit 1 derived from glycidyl methacrylate, structural unit 2 derived from styrene, and structural unit 3 derived from tricyclodecanyl methacrylate = 60 / 10 / 30 (mol%) obtained by reacting acrylic acid with the glycidyl groups of the structural unit.

[0175] "Alkali-soluble acrylic resin solution C": A 30% solids solution of a copolymer of styrene / α-methylstyrene / acrylic acid = 70 / 10 / 20 (mol ratio) in PGMEA. Weight average molecular weight: 4600, acid value of the solids excluding the solvent: 108 mg KOH / g.

[0176] "Fluorene acrylate solution A": a PGMEA solution (solid content 50% by weight) of the compound represented by formula (19). This is component (a) and corresponds to the compound represented by formula (3).

[0177] [ka]

[0178] "Fluorene acrylate solution B": a PGMEA solution (solid content 50% by weight) of the compound represented by formula (20). This is component (a) and corresponds to the compound represented by formula (3).

[0179] [ka]

[0180] "Fluorene acrylate solution C": a PGMEA solution (solid content 50% by weight) of the compound represented by formula (21). This is component (a) and corresponds to the compound represented by formula (5).

[0181] [ka]

[0182] "Fluorene acrylate solution D": a PGMEA solution (solid content 50% by weight) of the compound represented by formula (22). This is component (a) and corresponds to the compound represented by formula (5).

[0183] [ka]

[0184] "Fluorene methacrylate solution E": a PGMEA solution (solid content 50% by weight) of the compound represented by formula (23). This is component (a) and corresponds to the compound represented by formula (5).

[0185] [ka]

[0186] "Fluorene acrylate solution F": a PGMEA solution (solid content 50% by weight) of the compound represented by formula (24). This is component (a) and corresponds to the compound represented by formula (5).

[0187] [ka]

[0188] "Fluorene acrylate solution G": A PGMEA solution (solid content 50% by weight) containing a compound represented by formula (24) / a compound represented by formula (25) at a weight ratio of 1 / 1. This is component (a) and corresponds to a mixture of a compound represented by formula (5) and an ammonium salt of the compound represented by formula (5).

[0189] [ka]

[0190] "Fluorene acrylate solution H": a PGMEA solution (solid content 50% by weight) of the compound represented by formula (26). This is component (a) and corresponds to the compound represented by formula (5).

[0191] [ka]

[0192] "Fluorene acrylate solution I": a PGMEA solution of the compound represented by formula (27) (solid content 50% by weight, OGSOL EA-0250P (Osaka Gas Chemicals Co., Ltd.)). It is a compound with the same structure as A-BPEF (manufactured by Shin-Nakamura Chemical Co., Ltd.) disclosed in Patent Document 1 and Oxol 0200A (manufactured by Osaka Gas Chemicals Co., Ltd.) disclosed in Patent Document 2, and is a compound that does not belong to component (a).

[0193] [ka]

[0194] "Fluorene acrylate solution J": A PGMEA solution (solid content 50 wt%) of the compound represented by formula (28). This is the same compound as FLN-5 disclosed in Patent Document 1, and is a compound that does not belong to component (a).

[0195] [ka]

[0196] "Fluorene acrylate solution K": A PGMEA solution (solid content 50% by weight) of the compound represented by formula (29). This compound has one 9,9-bisarylfluorene skeleton in the molecule and two partial structures with carboxyl groups derived from dicarboxylic acid anhydride in the molecule, and is a compound that does not belong to component (a).

[0197] [ka]

[0198] "Fluorene acrylate solution L": A PGMEA solution (solid content 50% by weight) of the compound represented by formula (30). This is a fluorene compound that does not have a 9,9-bisarylfluorene skeleton, and is a compound that does not belong to component (a).

[0199] [ka]

[0200] (Synthesis Example 1: Synthesis of "Polymer-type Dispersant Solution B") A mixture of 12.91 g of methacrylic acid (0.15 mol), 55.07 g of methyl methacrylate (0.55 mol), 21.01 g of acid phosphoxyethyl methacrylate (0.10 mol), 26.43 g of benzyl methacrylate (0.15 mol), and 8.21 g of azobisisobutyronitrile was added dropwise over 30 minutes to 185.44 g of PGMEA maintained at a liquid temperature of 100 ° C. The mixture was stirred for 1 hour while maintaining the liquid temperature at 100 ° C., and then cooled to obtain a PGMEA solution of a methacrylic copolymer with a weight average molecular weight (Mw) of 9500 and phosphate groups in the side chains. This solution was diluted with PGMEA to a solids content of 30 wt% to obtain polymer dispersant solution B.

[0201] (Synthesis Example 2: Synthesis of "alkali-soluble polyimide resin B") Under a dry nitrogen stream, 31.13 g (0.085 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.24 g (0.0050 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 2.18 g (0.02 mol) of 3-aminophenol were dissolved in 150.00 g of N-methylpyrrolidone in a three-neck flask. A solution of 31.02 g of oxydiphthalic anhydride dissolved in 50.00 g of N-methylpyrrolidone was added to the flask, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. 15 g of xylene was then added, and the mixture was stirred at 150°C for 5 hours while azeotroping the by-product water with the xylene. After the reaction was complete, the reaction solution was poured into 3 L of deionized water, and the resulting solid precipitate was collected by filtration. The obtained solid precipitate was washed three times with deionized water and then dried in a vacuum dryer at 80°C for 24 hours to obtain alkali-soluble polyimide resin B. Alkali-soluble polyimide resin B was in powder form with a solid content of 100% and had a weight-average molecular weight (Mw) of 27,000.

[0202] (Synthesis Example 3: Synthesis of "Adamantane Acrylate Solution 1") In a three-neck flask, 123.79 g of PGMEA as a solvent was added under a dry nitrogen stream. 147.20 g (0.30 mol) of a compound represented by formula (55) (manufactured by Idemitsu Kosan Co., Ltd.), 43.24 g (0.60 mol) of acrylic acid (Tokyo Chemical Industry Co., Ltd.), 0.17 g (1.12 mmol) of tetramethylammonium bromide (Tokyo Chemical Industry Co., Ltd.) as a phase transfer catalyst, and 0.04 g (0.35 mmol) of methoquinone (Tokyo Chemical Industry Co., Ltd.) as a thermal polymerization inhibitor were added, and the liquid temperature was raised to 60 °C and stirred for 10 minutes. Next, the liquid temperature was raised to 100 °C and heated under reflux with stirring for 9 hours to obtain a solution containing an intermediate reaction product, which was epoxy acrylate (first reaction step). Next, 45.64 g (0.30 mol) of 1,2,3,6-tetrahydrophthalic anhydride was added, and the liquid temperature was heated at 90 °C for 12 hours to obtain a solution containing the target reaction product (second reaction step). This was dried under reduced pressure for 10 hours to obtain 200.00 g of white powder, which was then dissolved in 2000.00 g of toluene as a solvent. The solution was passed through silica gel chromatography to obtain a toluene solution containing only the compound represented by formula (56). This was then dried under reduced pressure for 10 hours to obtain the compound represented by formula (56) in the form of a white powder. A PGMEA solution (solid content 50 wt%) of the compound represented by formula (56) was prepared and designated adamantane acrylate solution 1. The compound represented by formula (56) is component (a) and corresponds to the compound represented by formula (40).

[0203] [ka]

[0204] [ka]

[0205] (Synthesis Example 4: Synthesis of "Adamantane Acrylate Solution 2") A compound represented by formula (58) was obtained in the same manner as in Synthesis Example 3, except that 106.94 g (0.30 mol) of a compound represented by formula (57) (manufactured by Idemitsu Kosan Co., Ltd.) was used instead of the compound represented by formula (55). A PGMEA solution (solid content 50 wt%) of the compound represented by formula (58) was prepared and named adamantane acrylate solution 2. The compound represented by formula (58) is component (a) and corresponds to the compound represented by formula (40).

[0206] [ka]

[0207] [ka]

[0208] (Synthesis Example 5: Synthesis of "Adamantane Acrylate Solution 3") A compound represented by formula (60) was obtained in the same manner as in Synthesis Example 3, except that 173.64 g (0.30 mol) of a compound represented by formula (59) (manufactured by Idemitsu Kosan Co., Ltd.) was used instead of the compound represented by formula (55). A PGMEA solution (solid content 50 wt%) of the compound represented by formula (60) was prepared and named adamantane acrylate solution 3. The compound represented by formula (60) is component (a) and corresponds to the compound represented by formula (40).

[0209] [ka]

[0210] [ka]

[0211] (Synthesis Example 6: Synthesis of "Adamantane Acrylate Solution 4") The compound represented by formula (61) was obtained in the same manner as in Synthesis Example 3, except that the amount of 1,2,3,6-tetrahydrophthalic anhydride added was changed to 91.28 g (0.60 mol) and the solution was passed through silica gel chromatography to obtain a toluene solution containing only the compound represented by formula (61). 1 Analysis by 1 H-NMR and LC-MS showed that no component (a) was produced in the solution after the second reaction step. A solution of the compound represented by formula (61) in PGMEA (solid content: 50 wt %) was prepared and designated as adamantane acrylate solution 4.

[0212] [ka]

[0213] (Synthesis Example 7: Synthesis of "Fluorene Acrylate Solution M") Under a dry nitrogen stream, 138.77 g (0.30 mol) of the compound represented by formula (62) (Osaka Gas Chemicals Co., Ltd.), 43.24 g (0.60 mol) of acrylic acid, 0.17 g (1.12 mmol) of tetramethylammonium bromide, and 0.04 g (0.35 mmol) of methoquinone were added to 118.30 g of PGMEA in a three-neck flask, and the liquid temperature was raised to 60°C and stirred for 10 minutes. Next, the liquid temperature was raised to 100°C and heated under reflux with stirring for 12 hours to obtain a solution containing the compound represented by formula (63) (first reaction step only). A PGMEA solution (solid content 50 wt %) of the compound represented by formula (63) was prepared and designated as fluorene acrylate solution M. The compound represented by formula (63) is not a compound belonging to component (a).

[0214] [ka]

[0215] [ka]

[0216] (Preparation Example 1: Preparation of Pigment Dispersion Liquid 1) 785.17g of PGMEA solvent was mixed with 9.60g of non-polymeric dispersant 1 and 35.80g of polymeric dispersant A and stirred for 5 minutes, after which 49.43g of ZCR-1569H was added and stirred for 10 minutes. (c) Pigment (40.00g) S0100, 40.00g CI Pigment Red 177, and 40.00g CI Pigment Blue 60) were added in that order and stirred for 30 minutes to obtain a pre-mixed solution. The pre-mixed solution was then pumped into a bead mill containing 0.4mm diameter zirconia beads at a 75% volumetric filling rate, and a wet media dispersion process was performed using a circulation system at a peripheral speed of 8m / s for 1 hour. The liquid was then sent to a bead mill filled with 0.05 mm diameter zirconia beads at a vessel filling rate of 75% by volume, and subjected to a wet media dispersion process using a circulation system at a peripheral speed of 8 m / s for 4 hours to prepare Pigment Dispersion 1 with a solids content of 20.00 wt%. Pigment Dispersion 1 has a solids content of 20.00 wt%, and the weight ratio of pigment / non-polymeric dispersant / polymeric dispersant / alkali-soluble resin is 60.00 / 4.80 / 17.90 / 17.30. The blend weights of each raw material are shown in Table 1.

[0217] [Table 1]

[0218] (Preparation Example 2: Preparation of Pigment Dispersion Liquid 2) Pigment dispersion 2 was obtained in the same manner as in Preparation Example 2, except that non-polymeric dispersant 2 was used instead of non-polymeric dispersant 1. Pigment dispersion 2 had a solids content of 20.00% by weight, and a weight ratio of pigment / non-polymeric dispersant / polymeric dispersant / alkali-soluble resin = 60.00 / 4.80 / 17.90 / 17.30. The blend weights of each raw material are shown in Table 1.

[0219] (Preparation Example 3: Preparation of Pigment Dispersion 3) 9.60 g of non-polymeric dispersant 3 and 119.33 g of polymeric dispersant solution B were mixed with 701.64 g of PGMEA solvent and stirred for 5 minutes, after which 49.43 g of ZCR-1569H was added and stirred for 10 minutes. 40.00 g of S0100, 40.00 g of CI Pigment Red 177, and 40.00 g of CI Pigment Blue 60 were added in that order and stirred for 30 minutes to obtain a preliminary mixed solution. The remaining steps were carried out in the same manner as in Preparation Example 1 to prepare Pigment Dispersion 3 with a solids content of 20.00 wt%. Pigment Dispersion 3 had a solids content of 20.00 wt% and a weight ratio of organic pigment / non-polymeric dispersant / polymeric dispersant / alkali-soluble resin of 60.00 / 4.80 / 17.90 / 17.30. The blend weight of each raw material is shown in Table 1.

[0220] (Preparation Example 4: Preparation of Pigment Dispersion Liquid 4) Pigment Dispersion 4 was prepared in the same manner as in Preparation Example 1, except that S0100 was not used and 60.00 g of CI Pigment Red 177 and 60.00 g of CI Pigment Blue 60 were used as the (c) pigments. Pigment Dispersion 4 had a solids content of 20.00 wt % and a weight ratio of organic pigment / non-polymeric dispersant / polymeric dispersant / alkali-soluble resin = 60.00 / 4.80 / 17.90 / 17.30. The blend weights of each raw material are shown in Table 1.

[0221] (Preparation Example 5: Preparation of Pigment Dispersion Liquid 5) 34.50 g of SOLSPERSE 20000 (Lubrizol; solids content: 100 wt%), a polymeric dispersant, and 782.00 g of MBA, a solvent, were mixed and stirred for 10 minutes. After that, 103.50 g of SO100 was added and stirred for 30 minutes. Using a horizontal bead mill packed with 0.40 mm zirconia beads, a wet media dispersion process was performed to obtain Pigment Dispersion 5, so that the number average particle diameter was 100 nm. Pigment Dispersion 5 had a solids content of 15.00 wt%, with a weight ratio of organic pigment to polymeric dispersant of 75 / 25. The blend weights of each raw material are shown in Table 1. Based on the method described in Patent Document 1, the number average particle diameter of the pigment contained in Pigment Dispersion 5 was measured using a Zetasizer Nano ZS (Sysmex Corporation) zeta potential / particle size / molecular weight analyzer, and was found to be 100 nm.

[0222] Example 1 Under yellow light, 0.38 g of NCI-831E (a photopolymerization initiator) was added to a mixed solvent of 6.38 g of MBA and 19.01 g of PGMEA and stirred for 10 minutes to dissolve. To this mixture, 1.27 g of fluorene acrylate solution A (component (a)), 5.14 g of SPC-3410 (component (e)), and 0.95 g of DPCA-60 (component (f)) (solids content: 100 wt%) were added and stirred to obtain a formulation. 16.88 g of pigment dispersion 1 was added to this formulation and stirred for 30 minutes to prepare negative-tone photosensitive composition 1 with a solids content of 15.00 wt%. The blend weights of each raw material are shown in Table 2. The particle size distribution of negative-tone photosensitive composition 1 was measured using the method described above, and the calculated XY values ​​are shown in Table 3.

[0223] [Table 2]

[0224] [Table 3]

[0225] Negative photosensitive composition 1 was applied to the surface of a transparent glass substrate, "Tempax" (manufactured by AGC Technoglass Co., Ltd.), using a spin coater, adjusting the rotation speed so that the final thickness of the cured film would be 1.5 μm, to obtain a coating film. The coating film was prebaked at 100°C under atmospheric pressure for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, the g, h, and i mixed rays of an ultra-high pressure mercury lamp were measured using the method described above. The entire surface of the prebaked film was irradiated with the optimal exposure dose without using a negative exposure mask to obtain an exposed film. The film was then developed, rinsed, and dried in the same manner as when calculating the optimal exposure dose, yielding a solid developed film. The developed film was heated in air at 230°C for 30 minutes using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a substrate for optical density evaluation with a 1.5 μm-thick solid cured film. The optical density (OD / μm) was evaluated using the method described above. The evaluation results are shown in Table 3.

[0226] Furthermore, a pixel dividing layer made of a cured film containing the cured product of the negative photosensitive composition 1, and a bottom-emission organic EL display device having the pixel dividing layer were produced by the following method.

[0227] FIG. 1 shows the steps of manufacturing an organic EL display device, including the step of forming a pixel dividing layer.

[0228] A silver alloy film (99.00 wt.% silver and 1.00 wt.% copper) was formed on the entire surface of an alkali-free glass substrate 1 measuring 70 mm long and 70 mm wide by sputtering. Using an alkali-soluble novolac-based positive resist, the substrate was immersed in silver alloy etching solution SEA-1 at a solution temperature of 30°C and etched to obtain a 50 nm-thick patterned silver alloy film 2. Furthermore, an ITO film was formed on the entire surface by sputtering. The alkali-soluble novolac-based positive resist was immersed in a 5 wt.% oxalic acid solution at a solution temperature of 50°C for 5 minutes, shower-washed with deionized water for 2 minutes, dried with an air blower, and heated at 200°C for 30 minutes in a dry nitrogen atmosphere to obtain a 10 nm-thick patterned ITO film 3. Through these processes, a first electrode-formed substrate was obtained, comprising a first electrode consisting of a silver alloy film / ITO film laminate pattern on the surface of the alkali-free glass substrate.

[0229] Negative photosensitive composition 1 was applied to the surface of a first electrode-forming substrate using a spin coater, adjusting the rotation speed so that the final pixel division layer thickness was 1.5 μm, to obtain a coating film. The coating film was then prebaked at 100°C under atmospheric pressure for 120 seconds using a hot plate to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, the prebaked film was pattern-exposed through a negative exposure mask (220 openings, 260 μm long and 70 μm wide) at the optimal exposure dose determined by the above-mentioned method to obtain an exposed film. The film was then developed, rinsed, and dried in the same manner as when calculating the optimal exposure dose to obtain a patterned developed film. The developed film was heated in a high-temperature inert gas oven at 230°C under air for 30 minutes to obtain a pixel division layer-forming substrate having a 1.5 μm-thick pixel division layer 4 with 220 openings within a 30 mm long x 30 mm wide area in the center of the first electrode-forming substrate. Two pixel division layer-forming substrates were produced using the above procedure, one of which was used to evaluate the taper angle of the pixel division layer, and the other was used to fabricate an organic EL display device. The evaluation results of the taper angle evaluated using the above method are shown in Table 3.

[0230] Next, the organic EL layer 5 including the light-emitting layer is formed in the opening of the pixel dividing layer 4 by vacuum deposition. -3Under evaporation conditions of 0.1 Pa or less, the pixel dividing layer forming substrate was rotated relative to the evaporation source. First, a 10 nm thick film of compound (HT-1) represented by formula (31) was formed as a hole injection layer, and a 50 nm thick film of compound (HT-2) represented by formula (32) was formed as a hole transport layer. Next, a 40 nm thick film of compound (GH-1) represented by formula (33) was evaporated onto the emitting layer as a host material, and a 40 nm thick film of compound (GD-1) represented by formula (34) was evaporated onto the emitting layer. Next, a 1:1 volume ratio of compound (ET-1) represented by formula (35) and compound (LiQ) represented by formula (36) was laminated as an electron transport material to a thickness of 40 nm.

[0231] [ka]

[0232] [ka]

[0233] [ka]

[0234] [ka]

[0235] [ka]

[0236] [ka]

[0237] Next, a 2-nm thick layer of LiQ was deposited, followed by deposition of a 150-nm thick silver / magnesium alloy (volume ratio 10:1) to form the second electrode 6. The substrate was then sealed by attaching a cap-shaped glass plate using an epoxy resin adhesive under a low-humidity, nitrogen atmosphere, to obtain an organic EL display device. The layers constituting the organic EL layer 5 are significantly thinner than the pixel division layer described above, and a stylus-type film thickness measurement device cannot provide high measurement accuracy. Therefore, each layer was measured using a quartz crystal oscillator film thickness monitor, which is suitable for thin films less than 100 nm thick. The film thickness was determined by rounding the average of three in-plane measurements to the nearest decimal place. The driving voltage of the fabricated organic EL display device was evaluated using the method described above. The evaluation results are shown in Table 3.

[0238] Examples 2 to 8 Negative-type photosensitive compositions 2 to 8 were prepared in the same manner as in Example 1 using fluorene acrylate solutions B to D, fluorene methacrylate solution E, and fluorene acrylate solutions F to H in the amounts shown in Tables 2 and 4, respectively, instead of fluorene acrylate solution A. The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. The evaluation results are shown in Tables 3 and 5.

[0239] [Table 4]

[0240] [Table 5]

[0241] Examples 9 to 11 Negative-type photosensitive compositions 9 to 11 were prepared in the same manner as in Example 1, except that fluorene acrylate solution D was used instead of fluorene acrylate solution A, and pigment dispersions 2 to 4 were used instead of pigment dispersion 1, in the amounts shown in Table 4. The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. The evaluation results are shown in Table 5.

[0242] (Comparative Examples 1 to 5) Negative-type photosensitive compositions 12 to 16 were prepared in the same manner as in Example 1, using fluorene acrylate solutions I to L instead of fluorene acrylate solution A in the amounts shown in Table 6. The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. The evaluation results are shown in Table 7.

[0243] [Table 6]

[0244] [Table 7]

[0245] (Comparative Example 6) Under yellow light, 0.57 g of NCI-831E was added to a mixed solvent of 6.38 g of MBA and 23.20 g of PGMEA and stirred for 10 minutes to dissolve. To this mixture, 3.08 g of alkali-soluble polyimide resin B, 0.95 g of fluorene acrylate solution I, and 1.18 g of KAYARAD DPHA were added and stirred to obtain a formulation. This formulation was then mixed with 14.65 g of pigment dispersion 5 and stirred for 30 minutes to prepare negative-tone photosensitive composition 17 with a solids content of 15.00 wt %. The blend weights of each raw material are listed in Table 8. An attempt was made to determine the optimal exposure dose for negative-tone photosensitive composition 17, but this was difficult due to insufficient solubility in the unexposed areas, making it impossible to obtain a patterned developed film. That is, when negative photosensitive composition 17 was evaluated using a low-concentration inorganic alkaline aqueous solution of 0.04 wt % potassium hydroxide as the developer, a pixel dividing layer could not be formed due to insufficient solubility.

[0246] [Table 8]

[0247] (Comparative Example 7) The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated for negative-type photosensitive composition 17 using the same method as in Example 1, except that a 2.38 wt % aqueous solution of tetramethylammonium hydroxide was used instead of the 0.04 wt % aqueous solution of potassium hydroxide. The evaluation results are shown in Table 9. That is, compared to Comparative Example 6, negative-type photosensitive composition 17 was evaluated using a 2.38 wt % aqueous solution of tetramethylammonium hydroxide, a high-concentration organic alkaline aqueous solution, as the developer, and a pixel dividing layer could be formed by changing the developer.

[0248] [Table 9]

[0249] (Comparative Example 8) Under yellow light, 0.53 g of OXE01 was added to 23.59 g of PGMEA and stirred for 10 minutes to dissolve. To this, 8.43 g of alkali-soluble acrylic resin solution C, 1.13 g of fluorene acrylate solution I, and 1.69 g of KAYARAD DPHA were added and stirred to obtain a formulation. This formulation was mixed with 14.65 g of pigment dispersion 5 and stirred for 30 minutes to prepare negative-type photosensitive composition 18 with a solids content of 15.00 wt%. The blend weights of each raw material are shown in Table 8. The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated for negative-type photosensitive composition 18 using the same methods as in Example 1. The evaluation results are shown in Table 9.

[0250] (Examples 12 to 15) Negative-type photosensitive compositions 19 to 22 were prepared in the same manner as in Example 1, using adamantane acrylate solutions 1 to 3 instead of fluorene acrylate solution A in the amounts shown in Table 10. The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. The evaluation results are shown in Table 11. Note that only negative-type photosensitive composition 22 was prepared by adding triphenylphosphine, which corresponds to the compound represented by formula (54).

[0251] [Table 10]

[0252] [Table 11]

[0253] (Comparative Example 9) Negative-type photosensitive composition 23 was prepared in the same manner as in Example 1, using adamantane acrylate solution 4 instead of fluorene acrylate solution A in the amounts shown in Table 12. The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. The evaluation results are shown in Table 13.

[0254] (Comparative Example 10) Negative photosensitive composition 24 was prepared in the same manner as in Example 1, without using fluorene acrylate solution A, in the amounts shown in Table 12. The optical density of the cured film, the XY values, the taper angle of the pixel dividing layer, and the driving voltage of the organic EL display device were evaluated. The evaluation results are shown in Table 13.

[0255] (Comparative Example 11) Negative-type photosensitive composition 25 was prepared in the same manner as in Example 1, without using fluorene acrylate solution A, in the amounts shown in Table 12. The optical density of the cured film, the XY values, and the taper angle of the pixel dividing layer were evaluated. The evaluation results are shown in Table 13. Note that one or more unlit pixels occurred, making it difficult to properly evaluate the driving voltage of the organic EL display device.

[0256] [Table 12]

[0257] [Table 13]

[0258] In Examples 1 to 15, developed films free from undercuts and pixel dividing layers with low taper angles were obtained by photolithography including a development step using a low-concentration inorganic alkaline aqueous solution, and yet the driving voltage required to obtain the desired luminance in an organic EL display device was low, making them superior to Comparative Examples 1 to 11. The above results demonstrate the usefulness of the negative-type photosensitive composition of the present invention. [Explanation of symbols]

[0259] 1: Alkali-free glass substrate 2: Silver alloy film 3: ITO film 4: Pixel division layer 5: Organic EL layer 6:Second electrode 7: Alkali-free glass substrate 8:ITO film / silver alloy film 9: Pixel division layer

Claims

1. (a) a (meth)acrylate compound having only one 9,9-bisarylfluorene skeleton in the molecule, having only one structure represented by formula (1) in the molecule, and having two methacryloxy groups and two acryloxy groups in total; (b) a photopolymerization initiator; and (c) containing a pigment; A negative photosensitive composition, in which the weight average molecular weight (Mw) of a compound having a 9,9-bisarylfluorene skeleton is 847 or less. 【Chemistry 1】 (In formula (1), R １ represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents the bonding site with an oxygen atom.) 2. The negative photosensitive composition according to claim 1, wherein the compound having a 9,9-bisarylfluorene skeleton has a weight average molecular weight (Mw) of 755 to 847.

3. 3. The negative photosensitive composition according to claim 1, wherein the component (a) contains a compound represented by formula (3): 【Chemistry 2】 (In formula (3), a and b are integers, each independently representing 0 or 1. R ２ and R ３ each independently represents an ethylene group or a propylene group. c and d are integers, each independently representing 0 to 3; R ４ and R ５ each independently represents a hydrogen atom or a methyl group. R ６ and R ７ One of R is a hydrogen atom and the other is a structure represented by formula (4). ８ and R ９ each independently represents an alkyl group having 1 to 3 carbon atoms. e and f are integers, each independently representing 0 to 2. 【Transformation 3】 (In formula (4), R １０ represents a divalent hydrocarbon group having 2 to 8 carbon atoms. * represents the bonding site with an oxygen atom.)

4. 4. The negative photosensitive composition according to claim 1, wherein the component (a) contains a compound represented by formula (5): 【Chemistry 4】 (In formula (5), R １１ and R １２ each independently represents a hydrogen atom or a methyl group. R １３ and R １４ R represents a structure represented by formula (6), a structure represented by formula (7), or a structure represented by formula (8). １５ and R １６ represents a methyl group; g and h are integers, each independently representing 0 to 2. 【Transformation 5】 【Transformation 6】 【Transformation 7】 (In formulas (6) to (8), * represents the bonding site with the oxygen atom.)

5. 5. The negative photosensitive composition according to claim 1, wherein the pigment (c) comprises a lactam-based organic black pigment.

6. 6. The negative photosensitive composition according to claim 5, further comprising (d) a pigment dispersant, wherein the pigment dispersant comprises a compound having a structure represented by formula (12). 【Transformation 8】 (In formula (12), R １７ represents a divalent hydrocarbon group. １８ represents a sulfo group or an N,N-dialkylamino group. * represents a bonding site.)

7. 7. The negative photosensitive composition according to claim 5, wherein, in a particle size distribution of all particle components contained in the negative photosensitive composition measured by a dynamic light scattering method, a cumulative 50% particle diameter X (nm) based on light scattering intensity and a cumulative 50% particle diameter Y (nm) based on volume satisfy the relationship 10 nm<X−Y<30 nm.

8. The negative photosensitive composition according to any one of claims 1 to 7, further comprising (g) a compound represented by formula (54): 【Chemistry 9】 (In formula (54), n ９ ~n １１ are integers, each independently representing 0 to 2. R ３３ ~R ３５ each independently represents a methyl group, an ethyl group, a methoxy group, or an ethoxy group.

9. A cured film comprising a cured product of the negative photosensitive composition according to any one of claims 1 to 8.

10. An organic EL display device comprising the cured film according to claim 9 .

11. 9. A method for producing a cured film, comprising: a coating step of applying the negative photosensitive composition according to claim 1 to obtain a coating film; an exposure step of exposing the composition to actinic radiation in a pattern to obtain an exposed film having exposed areas and unexposed areas in its plane; a development step of developing the composition with an alkaline developer containing potassium hydroxide to obtain a developed film; and a curing step of thermally curing the composition by heating to obtain a cured film.

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