Copolymer, photosensitive composition, cured product, and organic EL display device

Abstract

The present invention is a copolymer (a) containing a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (3), and a structural unit represented by formula (4), the copolymer (a) being characterized in that the total of the structural units represented by any one of formulae (1)-(4) is 70-100 mol% per 100 mol% of the total of all the structural units of the copolymer (a), and the content of the structural units represented by any one of formulae (1)-(4) in the copolymer (a) is 50-100 mol% per 100 mol% of the total of all the structural units of the copolymer (a). When the total number of moles of the structural unit represented by formula (1) and the structural unit represented by formula (2) is X, the number of moles of the structural unit represented by formula (3) is Y, and the number of moles of the structural unit represented by formula (4) is Z, the value A obtained by dividing X by Y is 1.0-10.0, and the value B obtained by dividing X by Z is 1.0-10.0.

Description

Technical Field

[0001] This invention relates to copolymers, photosensitive compositions, cured products, and organic EL display devices. Background Technology

[0002] In recent years, many products using organic electroluminescent (hereinafter referred to as "EL") display devices have been developed for thin display devices such as smartphones, tablets and televisions.

[0003] Typically, organic EL display devices have transparent electrodes such as indium tin oxide (hereinafter referred to as "ITO") on the light extraction side of the light-emitting element and metal electrodes such as an alloy of magnesium and silver on the non-light extraction side of the light-emitting element. In addition, in order to divide the pixels of the light-emitting element, an insulating layer such as a pixel division layer is formed between the transparent electrode and the metal electrode.

[0004] In recent years, efforts have been made to reduce the reflection of external light such as sunlight and improve the visual clarity and contrast of organic EL display devices by imparting light-blocking properties to the pixel segmentation layer. As a specific example, a negative photosensitive resin composition using black pigment has been disclosed (see, for example, Patent Documents 1 and 2).

[0005] Existing technical documents Patent Document 1: Japanese Patent Application Publication No. 2022-38599 Patent Document 2: International Publication No. 2022 / 230792 Summary of the Invention

[0006] The problem that the invention aims to solve However, regarding the negative photosensitive resin composition disclosed in Patent Document 1, although the absolute value of the difference between the pattern forming width and the mask design width (hereinafter sometimes referred to as "mask deviation") is small, there are the following problems: low reflow during the curing process, resulting in a high cone angle after curing; in addition, due to the thermal crosslinking groups, the tolerance (allowable range) for pre-baking temperature conditions is insufficient, resulting in tiny development residues at the opening of the pixel dividing layer, i.e., on the surface of the ITO electrode. Furthermore, regarding the negative photosensitive coloring resin composition disclosed in Patent Document 2, depending on the development method, there is a development pattern where the unexposed portion of the film is removed by finely peeling it off from the surface of the ITO electrode in an alkaline developing solution. The discharge of alkaline developing waste liquid containing numerous coarse, amorphous films increases the risk of contamination of the developing tank and pipe blockage, leaving room for improvement.

[0007] Methods for solving problems The inventors of this application have conducted repeated and in-depth research and discovered that copolymers comprising the following composition and photosensitive compositions containing such copolymers can solve the aforementioned problems.

[0008] [1] A copolymer, which is a copolymer (a) containing the following structural units: The structural unit represented by equation (1) and / or the structural unit represented by equation (2), The structural unit represented by equation (3) and The structural unit represented by equation (4) Of the total 100 mol% of all structural units of the copolymer (a), the total number of structural units represented by any one of formulas (1) to (4) is 70 to 100 mol%. In the aforementioned copolymer (a), when the total number of moles of the structural unit represented by formula (1) and the structural unit represented by formula (2) is set as X, the number of moles of the structural unit represented by formula (3) is set as Y, and the number of moles of the structural unit represented by formula (4) is set as Z, the value A obtained by dividing X by Y is 1.0~10.0, and the value B obtained by dividing X by Z is 1.0~10.0.

[0009] [Chemical Formula 1] In equation (1), R 1 Represents a hydrogen atom or a methyl group. R 2 Indicates a single bond or an alkylene group having 1 to 3 carbon atoms. n 1 It is an integer, and represents 1 or 2. R 3 Indicates an alkyl group or an alkoxy group having 1 to 3 carbon atoms. 2 It is an integer, and represents 0 to 2. Indicates the bonding site.

[0010] In equation (2), R 4 Represents a hydrogen atom or a methyl group. R 5 Indicates an alkylene group having 1 to 3 carbon atoms. 3 It is an integer, and represents 1 or 2. R 6 Indicates an alkyl group or an alkoxy group having 1 to 3 carbon atoms. 4 It is an integer, and represents 0 to 2. Indicates the bonding site.

[0011] In equation (3), R 7 It represents a hydrogen atom or a methyl group. Indicates the bonding site.

[0012] In equation (4), R 8 Represents a hydrogen atom or a methyl group. R 9 It refers to alkyl groups with 5 to 18 carbon atoms. Indicates the bonding site.

[0013] [2] The copolymer as described in [1] has a weight-average molecular weight (Mw) of 10,000 to 50,000.

[0014] [3] The copolymer as described in [1] or [2], wherein the copolymer (a) has a structural unit represented by the foregoing formula (1).

[0015] [4] The copolymer as described in any one of [1] to [3], wherein R in the foregoing formula (4) 9 is a branched alkyl group having 7 to 15 carbon atoms.

[0016] [5] The copolymer as described in any one of [1] to [4], wherein the copolymer (a) has a structural unit represented by formula (8).

[0017] [Chemical formula 2] In formula (8), R 14 and R 15 each independently represent a hydrogen atom or a methyl group, and R 16 represents a divalent group having 4 to 12 carbon atoms and having a hydroxyl group.

[0018] [6] The copolymer as described in [5], wherein, in a total of 100 mol% of all the structural units of the copolymer (a), the copolymer (a) contains 5 to 18 mol% of the structural unit represented by the foregoing formula (8).

[0019] [7] The photosensitive composition, which contains, in addition to the copolymer (a) described in any one of [1] to [6], a pigment, a photosensitizer, and an organic solvent.

[0020] [8] The photosensitive composition as described in [7], which further contains a (meth)acrylate compound having two 9,9-bis(naphthyl)fluorene skeletons in the molecule and having two ethylenically unsaturated double bond groups in the molecule, and has negative photosensitivity.

[0021] [9] The photosensitive composition as described in [7] or [8], which further contains a compound represented by formula (9) and has negative photosensitivity.

[0022] [Chemical formula 3] In formula (9), PO represents oxypropylene, EO represents oxyethylene, x, y, and z are each independently an integer of 1 to 50, and satisfy the relationship y < x + z.

[0023]

[10] The cured product is obtained by curing the photosensitive composition described in any one of [7] to [9].

[0024]

[11] An organic EL display device comprising the cured material described in

[10] .

[0025] Invention Effects The copolymers according to the present invention can ensure a wide tolerance range of pre-baking temperature conditions, suppress the generation of developing residues on the surface of ITO electrodes, obtain excellent solubility in high-concentration organic alkaline developing solutions, and impart high reflux properties to photosensitive compositions. Attached Figure Description

[0026] [ Figure 1 [A diagram showing the cone angle θ of the cured product (insulating layer 4) of the photosensitive composition] [ Figure 2 This is a photographic record showing one instance of a failure in the evaluation of the development morphology among all embodiments and comparative examples.

[0027] [ Figure 3 [Image] is a schematic diagram of the fabrication steps of the organic EL display device in the embodiment. Detailed Implementation

[0028] The present invention will now be described in detail.

[0029] The copolymer of the present invention is a copolymer (a) containing structural units represented by formula (1) and / or structural units represented by formula (2), structural units represented by formula (3), and structural units represented by formula (4).

[0030] [Chemical Formula 4] (In equation (1), R) 1 Represents a hydrogen atom or a methyl group. R 2 Indicates a single bond or an alkylene group having 1 to 3 carbon atoms. n 1 It is an integer, and represents 1 or 2. R 3 Indicates an alkyl group or an alkoxy group having 1 to 3 carbon atoms. 2 It is an integer, and represents 0 to 2. Indicates the bonding site.

[0031] In equation (2), R 4 Represents a hydrogen atom or a methyl group. R 5 Indicates an alkylene group having 1 to 3 carbon atoms. 3 It is an integer, and represents 1 or 2. R 6 Indicates an alkyl group or an alkoxy group having 1 to 3 carbon atoms. 4 It is an integer, and represents 0 to 2. Indicates the bonding site.

[0032] In equation (3), R 7 It represents a hydrogen atom or a methyl group. Indicates the bonding site.

[0033] In equation (4), R 8 Represents a hydrogen atom or a methyl group. R 9 It refers to alkyl groups with 5 to 18 carbon atoms. (Indicates the bonding site.) The structural unit in copolymer (a) refers to the structural unit of the monomer that has one unsaturated double bond group in the molecule when the copolymer is obtained.

[0034] As a copolymerization method for the copolymer (a) of the present invention, for example, the method described in Japanese Patent Application Publication No. 5-19467 can be used, and known methods can be used.

[0035] Examples of structural units represented by formula (1) include 4-hydroxyphenyl methacrylate (hereinafter referred to as PQMA), methyl methacrylate, ethyl methacrylate, propyl methacrylate, 4-hydroxyphenyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate.

[0036] Examples of structural units represented by formula (2) include 2-allylphenol, 4-allyl-2,6-dimethoxyphenol, 4-allyl-2,6-dimethylphenol, 4-allyl-2,6-diethylphenol, and 4-allyl-2,6-dipropylphenol.

[0037] By incorporating structural units represented by formula (1) and / or formula (2) into copolymer (a), an effect of inhibiting free radical chain reactions is achieved, for example, in a photosensitive composition containing copolymer (a), such as a negative photosensitive composition, resulting in reduced mask deviation and the formation of patterns as intended. Among these, copolymer (a) preferably has structural units represented by formula (1).

[0038] Examples of structural units represented by formula (3) include methacrylic acid (hereinafter referred to as MAA) and acrylic acid.

[0039] By making copolymer (a) contain the structural unit represented by formula (3), it is possible to impart alkaline developability to a photosensitive composition containing copolymer (a).

[0040] Examples of structural units represented by formula (4) include hexyl methacrylate, hexyl acrylate, 2-ethylhexyl methacrylate (hereinafter referred to as 2-EHMA), 2-ethylhexyl acrylate, n-octyl methacrylate, n-octyl acrylate, decyl methacrylate, decyl acrylate, isodecanyl methacrylate, isodecanyl methacrylate, 2-propylheptyl methacrylate, 2-propylheptyl methacrylate, dodecyl methacrylate, dodecyl methacrylate, undecyl methacrylate, undecyl methacrylate, isostearyl methacrylate, isostearyl methacrylate, stearyl methacrylate, stearyl methacrylate, etc.

[0041] By incorporating the structural unit represented by formula (4) into copolymer (a), high reflowability can be imparted to the photosensitive composition containing copolymer (a) during the heat curing process. Among these, copolymer (a) preferably has R in formula (4). 9 The structural unit is represented by a branched alkyl group with 7 to 15 carbon atoms.

[0042] Regarding the copolymer (a) of the present invention, in a total of 100 mol% of all structural units, there are structural units represented by any one of formulas (1) to (4) totaling 70 to 100 mol%. Furthermore, in the copolymer (a) of the present invention, when the total number of moles of structural units represented by formula (1) and formula (2) is set as X, the number of moles of structural units represented by formula (3) is set as Y, and the number of moles of structural units represented by formula (4) is set as Z, the value A (A=X / Y) obtained by dividing X by Y is 1.0 to 10.0, and the value B (B=X / Z) obtained by dividing X by Z is 1.0 to 10.0. By using structural units representing any of the formulas (1) to (4) totaling 70 to 100 mol%, the value A obtained by dividing X by Y is 1.0 to 10.0, and the value B obtained by dividing X by Z is 1.0 to 10.0, thereby ensuring good balance in mask deviation of the photosensitive composition containing copolymer (a), suppression of residues caused by pre-baking temperature conditions, and reflow in the heat curing process, and also obtaining excellent solubility in alkaline development.

[0043] The copolymer (a) of the present invention can also be copolymerized using any (meth)acrylic acid monomer as a monomer as needed. Specifically, it may include monomers with carboxyl groups such as itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid, 2-carboxyethyl acrylate oligomer, 2-carboxyethyl methacrylate oligomer, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, etc. Acrylates or methacrylates such as tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, etc., or their (fluoro)alkyl ester monomers; styrene, α-methylstyrene, 4-vinyltoluene and its structural isomers, 4-methoxystyrene and its structural isomers, 4-butoxystyrene and its structural isomers, 4-tert-butoxystyrene and its structural isomers, 4-vinylbiphenyl, 2-vinylnaphthalene and its structural isomers, 9-vinylanthracene, 9-vinylcarbazole, etc., unsaturated monomers with aromatic rings.

[0044] For the copolymer (a) of the present invention, it is also possible to further polymerize structural units having carboxyl groups, such as the structural unit represented by formula (3), itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid, 2-carboxyethyl acrylate oligomer, and 2-carboxyethyl methacrylate oligomer, and then introduce known structural units having olefinic unsaturated groups. For example, a method of adding a polymerizable unsaturated monomer containing a glycidyl group to a copolymer (a) having a structural unit represented by formula (3) can be cited. In this case, glycidyl acrylate, glycidyl methacrylate, etc., can be cited as examples of unsaturated monomers containing a glycidyl group. Especially when the photosensitive composition of the present invention described later has negative photosensitivity, it is preferable to have a structural unit represented by formula (8) from the viewpoint of suppressing the generation of developing residue caused by tiny pigments with a major diameter of less than 0.1 μm.

[0045] [Chemical Formula 5] (In equation (8), R) 14 and R 15 Each can independently represent a hydrogen atom or a methyl group, R 16 This refers to a divalent group with 4 to 12 carbon atoms that contains a hydroxyl group. Considering the need for repatriation, R 16 Preferably, it is a divalent group with 4 to 8 carbon atoms and a hydroxyl group, R 15 Methyl is preferred. R 16It can have oxygen atoms in the main chain, or it can have an alicyclic structure or an aromatic ring.

[0046] As a specific example of the structural unit represented by equation (8), structural units represented by equations (10) to (14) are preferred.

[0047] [Chemical Formula 6] From the perspective of simultaneously achieving the effect of suppressing the development residue of less than 0.1 μm on the surface of the ITO electrode and suppressing the residue of more than 0.1 μm at the pre-baking temperature of 130°C, thereby making the tolerance (allowable range) of the pre-baking temperature conditions wide, it is preferable to contain 5 to 18 mol% of the structural unit represented by the aforementioned formula (8) in a total of 100 mol% of all structural units of the aforementioned copolymer (a).

[0048] The weight-average molecular weight (Mw) of the copolymer (a) of the present invention is preferably 10,000 to 50,000. By making the weight-average molecular weight (Mw) 10,000 or more, even when the pre-baking temperature of the photosensitive composition containing the copolymer (a) is low, a moderately long development time can be ensured, and in the case of a negative photosensitive composition, the pattern can be prevented from becoming an inverted cone shape. On the other hand, by making the weight-average molecular weight (Mw) 50,000 or less, even when the pre-baking temperature is high (e.g., 130°C), the generation of opening residue can be suppressed.

[0049] The weight-average molecular weight (Mw) is a value obtained by analyzing a tetrahydrofuran-based gel permeation chromatography (GPC) sample using a standard curve based on standard polystyrene.

[0050] The copolymer (a) can be suitably used in the photosensitive composition. Regarding the content of the copolymer (a) in the photosensitive composition, from the viewpoint of high reflowability during the heat curing process and minimizing curing mask deviation, it is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to 100% by mass of the total components other than the solvent in the photosensitive composition. On the other hand, from the viewpoint of improving sensitivity during exposure, it is preferably 60% by mass or less, and more preferably 50% by mass or less.

[0051] Ideal results can be achieved by using the copolymer (a) of the present invention in a photosensitive composition containing pigment (b), photosensitizer (c) and organic solvent (d).

[0052] As the pigment (b) used in the photosensitive composition of the present invention, organic pigments and inorganic pigments commonly used in the field of electronic information materials can be used. Examples of organic pigments include, for example, diketopyrrolopyrrole pigments, azo, diazo or polyazo pigments, copper phthalocyanine, copper halide phthalocyanine or metal-free phthalocyanine pigments, anthraquinone, diaminodianthraquinone, anthraquinone, flavin anthrone, anthraquinone, indanone, pinantrone or anthrone violet pigments, quinacridone pigments, dioxazine pigments, violet ketone pigments, perylene pigments, thioindole pigments, isoindoline pigments, isoindoline ketone pigments, quinoline ketone pigments, vat pigments or metal complex pigments, etc.

[0053] Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, silica, alumina, kaolin clay, talc, bentonite, iron oxide black, cadmium red, iron oxide red, molybdenum chrome red, molybdenum chrome orange, chrome vermilion, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chrome green, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Prussian blue, cobalt blue, sky blue, cobalt silicon blue, cobalt zinc silicon blue, manganese violet, or cobalt violet.

[0054] As red pigments, examples include Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, or 254 (the values ​​are all dye index (hereinafter referred to as "CI") numbers).

[0055] As for pigments that are orange, examples include Pigment Orange 13, 36, 38, 43, 51, 55, 59, 61, 64, 65 or 71 (all values ​​are CI numbers).

[0056] Examples of yellow pigments include, for example, Pigment Yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, or 185 (all values ​​are CI codes).

[0057] Examples of purple pigments include, for example, Pigment Violet 19, 23, 29, 30, 32, 37, 40, or 50 (all values ​​are CI codes).

[0058] As for blue pigments, examples include Pigment Blue 15, 15:3, 15:4, 15:6, 22, 60, or 64 (all values ​​are CI codes).

[0059] As for green pigments, examples include pigments 7, 10, 36, or 58 (all values ​​are CI codes).

[0060] Examples of black pigments include, for example, black organic pigments, mixed organic pigments, or inorganic pigments. Examples of black organic pigments include, for example, carbon black, perylene black, aniline black, or benzofuranone pigments (described in Japanese Patent Publication No. 2012-515233).

[0061] By combining these pigments, it is also possible to obtain a photosensitive composition with the desired optical properties, but from the viewpoint of visible light shielding and insulation per unit mass, it is preferable to include benzofuranone pigments.

[0062] Regarding the content of pigment (b) in the photosensitive composition used in the present invention, from the viewpoint of light-blocking properties per unit film thickness, it is preferably 5% by mass or more, more preferably 10% by mass or more, relative to 100% by mass of the total components other than the solvent in the photosensitive composition. On the other hand, from the viewpoint of improved sensitivity during exposure and fine-line processing properties, it is preferably 50% by mass or less, more preferably 40% by mass or less.

[0063] The photosensitizer (c) used in the photosensitizing composition of the present invention may contain a photopolymerization initiator (c1), a photoacid generator (c2), etc. The photopolymerization initiator (c1) is a compound that generates free radicals by bond cleavage and / or reaction through exposure, and the photoacid generator (c2) is a compound that generates acid by light irradiation.

[0064] Regarding the photosensitive composition, by including a photopolymerization initiator (c1) and a free radical polymerizable compound described later, free radical polymerization can be carried out in the light-irradiated area, resulting in a negative raised pattern where the light-irradiated area becomes insoluble. On the other hand, by including a photoacid-generating agent (c2), acid is generated in the light-irradiated area, increasing the solubility of the light-irradiated area in an alkaline aqueous solution, resulting in a positive raised pattern where the light-irradiated area dissolves.

[0065] Examples of photopolymerization initiators (c1) include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-aminoalkylphenyl ketone-based photopolymerization initiators. Two or more of these may be included. Among them, carbazole-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred from the perspective of high sensitivity to mixed lines containing i-lines (365 nm), h-lines (405 nm), and g-lines (436 nm) in the exposure process described later.

[0066] Regarding the content of the photopolymerization initiator (C1) in the photosensitive composition of the present invention, from the viewpoint of improving exposure sensitivity, it is preferably 1% by mass or more, more preferably 5% by mass or more, relative to the content of the free radical polymerizable compound described later (100% by mass). On the other hand, from the viewpoint of fine-line processability, it is preferably 90% by mass or less, more preferably 80% by mass or less.

[0067] As a photoacid generator (C2), it may contain, for example, a quinone diazide compound.

[0068] As quinone diazide compounds, they can be compounds formed by ester bonds between quinone diazide sulfonic acid and polyhydroxy compounds, compounds formed by sulfonamide bonds between quinone diazide sulfonic acid and polyamino compounds, and compounds formed by ester bonds and / or sulfonamide bonds between quinone diazide sulfonic acid and polyhydroxy polyamino compounds.

[0069] As a quinone diazide structure, naphthoquinone diazide-5-sulfonyl or naphthoquinone diazide-4-sulfonyl is preferred. Naphthoquinone diazide sulfonate compounds may contain both naphthoquinone diazide-4-sulfonyl and naphthoquinone diazide-5-sulfonyl groups in the same molecule, or they may contain both naphthoquinone diazide-4-sulfonate and naphthoquinone diazide-5-sulfonate compounds. The naphthoquinone diazide-4-sulfonate compound exhibits absorption in the i-line region of the mercury lamp, making it suitable for i-line exposure. The absorption of the naphthoquinone diazide-5-sulfonate compound extends to the g-line region of the mercury lamp, making it suitable for g-line exposure.

[0070] The aforementioned quinone diazide compounds can be synthesized from compounds with phenolic hydroxyl groups and quinone diazide sulfonic acid compounds via optional esterification reactions. Using these quinone diazide compounds further improves resolution, sensitivity, and film retention.

[0071] From the viewpoint of high sensitivity, the content of photoacid generator (c2) is preferably 0.1% by mass or more, more preferably 10% by mass or more, and even more preferably 25% by mass or more, relative to 100% by mass of copolymer (a). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarization layer and / or insulating layer in an organic EL display device, the content of photoacid generator (c1) is preferably 100% by mass or less, relative to 100% by mass of copolymer (a).

[0072] As the organic solvent (d) used in the photosensitive composition of the present invention, for example, it may contain polar aprotic solvents such as γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, etc. Ethers, including dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, dioxane, etc.; acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, etc.; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, etc.; 2-hydroxy Ethyl 2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxypropionate, ethyl hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate The solvent may contain two or more of the following: isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, and N,N-dimethylisobutyramide; and 3-methyl-2-oxazolidinone.

[0073] The photosensitive composition of the present invention may contain a free radical polymerizable compound (e). In particular, when the above-mentioned photosensitive composition contains a photopolymerization initiator (c1), it must contain a free radical polymerizable compound (e).

[0074] From the viewpoint of improving sensitivity during exposure, the free radical polymerizable groups present in the free radical polymerizable compound (e) are preferably acryloyl or methacryloyl, and may contain two of them.

[0075] As a free radical polymerizable compound (e), it is preferably a compound having two or more free radical polymerizable groups. Examples include bisphenol A diglycidyl ether (meth)acrylate, poly(meth)acrylate urethane, modified bisphenol A epoxy (meth)acrylate, 1,6-hexanediol adipic acid (meth)acrylate, phthalic anhydride epoxy propylene oxide (meth)acrylate, trimellitic acid diethylene glycol (meth)acrylate, rosin-modified epoxy di(meth)acrylate, alkyd-modified (meth)acrylate, fluorene diacrylate oligomers, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylformal, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2,2-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]propane, bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]sulfone, bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]ether, 4,4'-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]sulfone Fluorine may contain two or more of the following: cyclohexane, 9,9-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-methyl-4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, bis[3-chloro-4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, biscresol fluorene diacrylate, biscresol fluorene dimethacrylate, etc.

[0076] From the perspective of maintaining the dissolved form during alkaline development and moderately controlling the cone angle after development to a low level, the photosensitive composition of the present invention preferably further contains a (meth)acrylate compound having two 9,9-bis(naphthyl)fluorene skeletons and two olefinic unsaturated double bond groups in the molecule, and has negative photosensitivity.

[0077] Regarding the content of the free radical polymerizable compound (e) in the photosensitive composition of the present invention, from the viewpoint of improving sensitivity during exposure, it is preferably 10% by mass or more, more preferably 15% by mass or more, relative to the total content of copolymer (a) and free radical polymerizable compound (e) of 100% by mass. On the other hand, from the viewpoint of reflowability during the heat curing process, it is preferably 80% by mass or less, more preferably 60% by mass or less.

[0078] The photosensitive composition of the present invention may further contain a dispersion resin (f) containing repeating units of general formula (5) having tertiary amino groups on their side chains, repeating units having carboxyl groups, and repeating units having olefinic unsaturated groups.

[0079] [Chemical Formula 7] In general formula (5), R 10 R represents a hydrogen atom or a methyl group. 11 R represents a single bond or an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom. 12 and R 13 Each can independently represent an alkyl or alkoxy group with 1 to 5 carbon atoms, an alicyclic hydrocarbon with 3 to 6 carbon atoms, or an aromatic hydrocarbon group with 6 to 10 carbon atoms. Indicates the bonding site.

[0080] Specifically, examples of monomers constituting the repeating unit represented by general formula (5) include 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2-dipropylaminoethyl acrylate, 2-diphenylaminoethyl acrylate, 2-dibenzylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dipropylaminoethyl methacrylate, 2-diphenylaminoethyl methacrylate, and 2-benzylaminoethyl methacrylate. These monomers can be used alone or in combination. By including an alkali-soluble resin having repeating units represented by general formula (5), tertiary amino groups are adsorbed onto the pigment surface, thereby further improving the storage stability of photosensitive compositions, such as negative photosensitive compositions.

[0081] Specifically, monomers constituting repeating units with carboxyl groups include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid, 2-carboxyethyl acrylate oligomers, and 2-carboxyethyl methacrylate oligomers.

[0082] As a method for synthesizing dispersion resin (f), a method can be adopted by polymerizing a structural unit represented by general formula (5), a unit containing a carboxyl group, and then further introducing a repeating unit having a known olefinic unsaturated group. For example, a method can be described by performing an addition reaction between a polymerizable unsaturated monomer containing a glycidyl group and a (meth)acrylic copolymer copolymer containing a carboxyl group. In this case, examples of carboxyl-containing unsaturated monomers for copolymerization include acrylic acid and methacrylic acid, and examples of glycidyl acrylate and glycidyl methacrylate are examples of glycidyl acrylate unsaturated monomers. These acrylic monomers can be used alone or in a mixture of two or more.

[0083] The acid value of the dispersion resin (f) is preferably 50-120 mg KOH / g. By setting it within this range, both pigment dispersion stability and solubility in alkaline developing solutions can be achieved simultaneously. Furthermore, the alkalinity is preferably 5-70 mmol / 100g. By setting it within this range, solubility in alkaline developing solutions can be maintained, and pigment dispersion stability can be improved. It should be noted that the alkalinity is defined as the number of moles of perchloric acid required to neutralize 100g of the dispersion resin (f).

[0084] Regarding the content of dispersion resin (f), from the viewpoint of pigment dispersion stability, it is preferably 5% by mass or more relative to the total mass of copolymer (a) and dispersion resin (f) of 100% by mass. On the other hand, from the viewpoint of minimizing mask deviation, it is preferably 50% by mass or less.

[0085] The photosensitive composition of the present invention may further contain a polymeric dispersant (g). The polymeric dispersant (g) refers to a substance possessing both an affinity group that has chemical bonding or adsorption effects on the pigment surface and a polymeric chain or group that has solubility, but does not contain olefinic unsaturated groups. Since the polymeric dispersant (g) does not contain olefinic unsaturated groups, there is a concern that adding large amounts may degrade the target photosensitivity; therefore, it is desirable to set an appropriate addition amount considering dispersion stability and photosensitivity. The polymeric dispersant (g) has the following effects: in the wet medium dispersion treatment described later, it improves the wettability of the pigment (b) to the dispersion medium, promotes the deagglomeration of the light-blocking material, stabilizes particle size and viscosity by utilizing steric hindrance and / or electrostatic repulsion effects, and thereby suppresses color separation of the photosensitive composition during storage or coating.

[0086] Examples of polymeric dispersants (g) include polyester-based, acrylic-based, polyurethane-based, polyallylamine-based, and carbodiimide-based dispersants. Among these, polymeric dispersants containing amino groups are preferred for improving the long-term storage stability of pigment dispersions.

[0087] The photosensitive composition of the present invention may contain a thermal crosslinking agent (h). A thermal crosslinking agent (h) refers to a compound having at least two thermally reactive functional groups such as alkoxymethyl, hydroxymethyl, epoxy, or oxetyl in its molecule. By containing a thermal crosslinking agent (h), crosslinking occurs between the thermal crosslinking agent (h) and the copolymer (a), or between the thermal crosslinking agents (h) themselves, thereby improving the heat resistance, chemical resistance, and flexural strength of the cured product after thermosetting.

[0088] Preferred examples of compounds having at least two alkoxymethyl or hydroxymethyl groups may include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML -HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), etc.

[0089] As preferred examples of compounds having at least two epoxy groups, they may contain "EPOLIGHT" (registered trademark) 40E, "EPOLIGHT" 100E, "EPOLIGHT" 200E, "EPOLIGHT" 400E, "EPOLIGHT" 70P, "EPOLIGHT" 200P, "EPOLIGHT" 400P, "EPOLIGHT" 1500NP, "EPOLIGHT" 80MF, "EPOLIGHT" 4000, "EPOLIGHT" 3002 (all manufactured by Kyoei Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L (all manufactured by Nagase). Chemtex (manufactured by Chemtex Co., Ltd.), GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), "Epikote" (registered trademark) 828, "Epikote" 1002, "Epikote" 1750, "Epikote" 1007, YX8100-BH30, E1256, E4250, E4275 (manufactured by Japan Epoxy Resin Co., Ltd.), "Epiclon" (registered trademark) EXA-9583, HP4032 (manufactured by DIC Co., Ltd.), VG3101 (manufactured by Mitsui Chemicals Co., Ltd.), "TEPIC" (registered trademark) S, "TEPIC" G, "TEPIC" P (manufactured by Nissan Chemical Industries, Ltd.), "Denacol" EX-321L (Nagase) Chemtex (manufactured by Chemtex Co., Ltd.), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), "Epotohto" (registered trademark) YH-434L (manufactured by Toto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), "Epiclon" (registered trademark) N695, HP7200 (all manufactured by DIC Co., Ltd.), etc.

[0090] As a compound having at least two oxocyclic butyl groups, it may contain, for example, ETERNACOLL EHO, ETERNACOLL OXBP, ETERNACOLL OXTP, ETERNACOLL OXMA (all manufactured by Ube Industries, Ltd.), oxocyclic butanol Novolac, etc.

[0091] It is possible to combine two or more thermal crosslinking agents (h).

[0092] The content of the thermal crosslinking agent (h) is preferably 1% by mass or more and 30% by mass or less in 100% by mass of the total amount of the photosensitive composition excluding the solvent. If the content of the thermal crosslinking agent (h) is 1% by mass or more in 100% by mass of the total amount of the photosensitive composition excluding the solvent, the chemical resistance of the cured product can be further improved. In addition, if the content of the thermal crosslinking agent (h) is 30% by mass or less in 100% by mass of the total amount of the photosensitive composition excluding the solvent, the storage stability of the photosensitive composition is excellent.

[0093] The photosensitive composition of the present invention preferably further contains a compound represented by the formula (9) as a residue inhibitor (i) and has negative photosensitivity.

[0094] [Chemical formula 8] (In the formula (9), PO represents oxypropylene, EO represents oxyethylene, x, y and z are each independently an integer of 1 to 50, and satisfy the relationship of y < x + z.) By containing the compound represented by the formula (9), residues smaller than 0.1 μm generated in the development process described later can be inhibited.

[0095] The photosensitive composition of the present invention may contain a surfactant, which can improve the wettability with the substrate. As the surfactant, for example, fluorine-based surfactants such as the SH series, SD series, ST series of Dow Corning Toray Co., Ltd., the BYK series of BYK Chemie Japan K.K., the KP series of Shin-Etsu Chemical Co., Ltd., the DISFOAM series of NOF Corporation, the "MEGAFACE (registered trademark)" series of DIC Corporation, the Fluorad series of Sumitomo 3M Ltd., the "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series of Asahi Glass Co., Ltd., the PolyFox series of OMNOVA Solutions Inc., etc., acrylic-based and / or methacrylic-based surfactants such as the Polyflow series of Kyoeisha Chemical Co., Ltd., the "DISPARLON (registered trademark)" series of Kusumoto Chemicals, Ltd., etc. can be contained.

[0096] When containing a surfactant, the content is preferably 0.001% to 1% by mass in 100% by mass of the total amount of the photosensitive composition excluding the solvent.

[0097] The photosensitive composition of the present invention may contain a nonionic surfactant as a leveling agent and a silane coupling agent as an adhesion improver for the substrate surface as needed.

[0098] The chemical structures of compounds belonging to the aforementioned copolymers (a), pigments (b), photosensitizers (c), organic solvents (d), free radical polymerizable compounds (e), dispersion resins (f), polymeric dispersants (g), and thermal crosslinking agents (h) can be analyzed by using the photosensitive composition of the present invention as a sample, combined with known analytical methods such as time-of-flight secondary ion mass spectrometry (TOF-SIMS), time-of-flight mass spectrometry (TOF-MS), nuclear magnetic resonance (NMR), liquid chromatography-mass spectrometry (LC-MS), gas chromatography-mass spectrometry (GC-MS), ICP mass spectrometry, infrared absorption spectroscopy, and X-ray diffraction. In particular, for pigments (b), the photosensitive composition can be centrifuged, and the concentrate obtained as the filter can be analyzed as a sample to improve identification accuracy. On the other hand, for copolymers (a) and photosensitizers (c), the filtrate obtained by filtering the supernatant after centrifugation can be analyzed as a sample to improve identification accuracy.

[0099] The method for preparing the photosensitive composition of the present invention is not particularly limited. For example, the following method can be used: a pigment dispersion containing pigment (b), dispersion resin (f), organic solvent (d), and polymeric dispersant (g) as needed is prepared in advance by wet dispersion treatment; then the copolymer (a), photosensitizer (c), organic solvent (d), free radical polymerizable compound (e) as needed, and other components are mixed and stirred with the pigment dispersion, and filtered as needed.

[0100] As a disperser for wet dispersion processing, it can be a wet media disperser or a wet media-free disperser. Considering the advantages of superior dispersion speed and economic efficiency, a wet media disperser is preferred. Examples of wet media dispersers include bead mills such as "Revomill" (registered trademark) (manufactured by Asada Iron Works Co., Ltd.), "Nanogetter" (registered trademark) (manufactured by Asizawa Finetech Co., Ltd.), "DYNO-MILL" (registered trademark) (manufactured by Willy A. Bachofen Co., Ltd.), "spike mill" (registered trademark) (manufactured by Inoue Manufacturing Co., Ltd.), "Sand Grinder" (registered trademark) (manufactured by DuPont Co., Ltd.), "ultra apex mill" (registered trademark) (manufactured by Hiroshima Metal & Machinery Co., Ltd.), and "NEO-AIMEX" (registered trademark) (manufactured by AIMEX Co., Ltd.). The preferred material for the media is ceramic beads such as zirconia, with a preferred diameter of 0.03 to 0.5 mm. As a commercially available product, "Torayceram" (registered trademark) (manufactured by Toray Industries, Inc.) is an example. When the primary particle size of pigment (b) and the particle size of the secondary particles formed by the aggregation of primary particles are small, a size of 0.03 to 0.10 mm is preferred. Tiny dispersed beads.

[0101] In this case, a bead mill with a diaphragm based on centrifugal separation is preferred, capable of separating tiny beads from the dispersion. On the other hand, when dispersing pigment (b) containing coarse particles at the submicron level, beads with a diameter of 0.10 mm or more are preferred to obtain sufficient grinding force. It should be noted that the bead diameter can be calculated by measuring the equivalent circle diameter of 100 randomly selected beads observed under a microscope and calculating their average value.

[0102] The cured product of the present invention is a cured product obtained by curing the aforementioned photosensitive composition. Here, "cured product" refers to a cured product obtained by heating the photosensitive composition at atmospheric pressure at a temperature of 200°C to 400°C for at least 10 minutes.

[0103] The organic EL display device of the present invention includes the aforementioned cured material. The organic EL display device includes at least a substrate, a first electrode, a second electrode, light-emitting pixels, a planarization layer, and a pixel segmentation layer. Preferably, it is an active-matrix type organic EL display device having a plurality of pixels formed in a matrix. In the active-matrix type display device, light-emitting pixels are provided on a substrate such as glass, and a planarization layer is provided to cover the light-emitting pixels and the lower portion of the area excluding the light-emitting pixels. Furthermore, the planarization layer has a first electrode provided to cover at least the lower portion of the light-emitting pixels, and a second electrode provided to cover at least the upper portion of the light-emitting pixels. Additionally, the active-matrix type display device has an insulating pixel segmentation layer for segmenting the light-emitting pixels, and the cured material obtained from the photosensitive composition of the present invention can be suitably used for the pixel segmentation layer.

[0104] Furthermore, the photosensitive composition of the present invention can form highly fine patterns that do not produce residue at the openings, and therefore can also be used for black matrices and black columnar spacers used in color filters for solid-state imaging devices, microLED and miniLED display devices.

[0105] The preferred embodiment of using the cured material of the present invention as a pixel partitioning layer in an organic EL display device will be described below. From the perspective of improving the value of the display device by suppressing external light reflection, the optical density per 1.0 μm film thickness of the pixel partitioning layer is preferably 0.8 or more, more preferably 1.0 or more. From the viewpoint of pattern processing, it is preferably 1.5 or less, more preferably 1.3 or less. Optical density refers to the value obtained by measuring the incident light intensity and transmitted light intensity of a pixel partitioning layer formed on a transparent substrate with a film thickness of 1.5 μm using an X-Rite 361T optical density meter (manufactured by X-Rite Corporation), calculating the optical density value (OD value) according to the following formula, and dividing the OD value by the film thickness value, i.e., 1.5; a higher optical density indicates higher light-blocking performance. As the transparent substrate, "Tempax (manufactured by AGC Techno Glass Co., Ltd.)" as a transparent glass substrate is preferably used.

[0106] Optical density = log 10 (I0 / I) In the above formula, I0: incident light intensity, I: transmitted light intensity.

[0107] From the perspective of suppressing electrode breakage and avoiding the generation of non-lit pixels, the cross-sectional cone angle at the inclined portion at the end of the pixel segmentation layer is preferably 50° or less, more preferably 45° or less. From the perspective of suppressing the reduction of light-shielding properties at the end of the thin film portion, it is preferably 20° or more, more preferably 25° or more. Here, the cone angle of the pixel segmentation layer is... Figure 1 The tilt angle θ of the end of the insulating layer 4 shown.

[0108] As a method for forming a pixel segmentation layer, a preferred method includes the following steps: a coating step, in which a photosensitive composition is coated to obtain a coated film; a pre-baking step, in which the coated film is heated to obtain a pre-baked film; an exposure step, in which active chemical rays are patterned and exposed through an exposure mask to obtain an exposed film; a developing step, in which an alkaline developer is used to develop the film to obtain a developed film; and a curing step, in which heat is used to thermally cure the film to obtain a cured product.

[0109] For coating equipment used in the coating process, spin coaters or slot coaters are preferred for their superior film coating properties. After coating, needle gap pre-baking or contact pre-baking can also be performed.

[0110] The pre-baking temperature in the pre-baking process is preferably 50~150℃, and the pre-baking time is preferably 30 seconds~5 minutes.

[0111] Examples of exposure apparatus used in the exposure process include steppers, mirror projection mask aligners (MPA), and parallel light mask aligners (PLA). Examples of active chemical rays used during exposure include the j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), or g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp. A mixed line containing at least the i-line is preferred, and a mixed line containing the g-line, h-line, and i-line is more preferable. The exposure mask can be a desired negative or positive mask. In the case of negative photosensitivity, the exposed portion solidifies and becomes insoluble in the developer. In the case of positive photosensitivity, the exposed portion dissolves in the developer.

[0112] As a developing method in the developing process, examples include spraying, immersion, and spin-dip methods, and a method of immersing the exposed film for 10 seconds to 3 minutes is also mentioned. From the perspective of reducing the amount of alkaline developer used and making the manufacturing process economically advantageous, the spin-dip method is preferred. As an alkaline developer, a 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as "TMAH") is preferred; commercially available examples include, for instance, 2.38% by mass TMAH (manufactured by Tama Chemical Industry Co., Ltd.). After the developing process, a cleaning treatment using deionized water spraying and / or a moisture removal treatment using air jetting may also be applied. Regarding the developing time, in the case of negative photosensitivity, from the perspective of eliminating uneven development of unexposed areas, it is preferable to set the developing time to 1.1 to 1.5 times the developing time when the film thickness of the unexposed area is 0 μm. When the film exhibits positive photosensitivity, considering the improvement of the in-plane uniformity of the film thickness of the developed film, it is preferable to set the film thickness to a value obtained by subtracting the thickness of the unexposed portion from the thickness of the pre-baked film, i.e., the film loss (μm) during the developing process, to be 1.0 μm or less. Considering the improvement of exposure sensitivity, it is preferable to set the film loss (μm) to be 0.5 μm or more. Alternatively, the flowability of the film during the curing process can be controlled by irradiating the obtained developed film with exposure light again as a second exposure process.

[0113] In the curing process, the developing film is thermally cured by heating, and residual developer and moisture in the film are evaporated to obtain a cured product. Examples of heating devices include hot air ovens and IR ovens, and the heating atmosphere can be nitrogen or air. The heating temperature is preferably 200-350°C at atmospheric pressure, more preferably 220-280°C.

[0114] Example The present invention is illustrated in detail by providing examples and comparative examples of negative photosensitive compositions, but the invention is not limited thereto.

[0115] <Evaluation Methods> (1) Weight-average molecular weight (Mw) The following value is the weight-average molecular weight (Mw) determined using gel permeation chromatography (GPC) "HLC-8220GPC" (a test apparatus of TOSOH Corporation), with tetrahydrofuran as the carrier and polystyrene as the molecular weight standard.

[0116] (2) Evaluation of the preparation of solidified materials Using a spin coater (MS-A150) manufactured by MIKASA Co., Ltd., three sheets of the photosensitive compositions obtained from the various examples and comparative examples were coated onto an ITO substrate with a cured film thickness of 1.5 μm. The three coated films were then pre-baked at 110°C, 120°C, and 130°C for 2 minutes each on a hot plate, resulting in 110°C pre-baked films, 120°C pre-baked films, and 130°C pre-baked films, respectively. For each pre-baked film, a mask aligner (PEM-6M) manufactured by Union Optical Co., Ltd. was used, with a negative mask (stripe design line width of 10 μm) placed between the films and the HOYA Co., Ltd. high-pressure mercury lamp as the light source, and a concentration of 200 mJ / cm² was applied. 2 Set to maximum exposure, at 10 mJ / cm² per interval. 2 The exposure was reduced in stages to achieve phased exposure. Next, each exposed film was developed using a small developing apparatus (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) and alkaline developer (2.38% TMAH aqueous solution by mass) via a spin-dip method. After rinsing with ultrapure water by spray for 60 seconds, the substrate was dried by idling at 1000 rpm for 30 seconds, resulting in a developed film with a striped pattern. The spin-dip method refers to spraying alkaline developer onto the surface of the exposed film for 10 seconds, then allowing it to stand for the specified development time. The development time was set to 1.3 times the time it takes for the unexposed portion of the film thickness to reach 0 μm. Next, each developed film was heated in air at 250°C for 1 hour using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured product with a striped pattern.

[0117] (3) Evaluation of development morphology The morphology of the exposure films obtained from each embodiment and comparative example during alkaline development by spin-dip and subsequent rinsing by spraying is observed visually. The development morphology is evaluated according to the following criteria: 0 is considered acceptable and × is considered unacceptable.

[0118] Development morphology 0: No film-like peeling is observed; the film is uniformly dissolved.

[0119] Development morphology ×: Observed Figure 2 The black, film-like peeling shown.

[0120] (4) Evaluation of pre-baking temperature tolerance For the developing films obtained from the various embodiments and comparative examples at three different pre-baking temperatures, the lowest exposure amount (mJ / cm²) that could be formed without peeling was observed using an optical microscope. 2 The presence or absence of granular residue larger than 0.1 μm within the opening of a striped pattern with a mask opening width of 10 μm is evaluated according to the following criteria. The less residue observed, the wider the pre-baking temperature tolerance, and the better the result. A and B are considered acceptable, and C is considered unacceptable.

[0121] A: No residue was observed in the developing films at three different pre-baking temperatures at all three levels.

[0122] B: Residue was observed at one of the three levels of developing films with different pre-baking temperatures.

[0123] C: Residue was observed at more than two levels of the developing films at three different pre-baking temperatures.

[0124] (5) Evaluation of mask deviation The cured products obtained from each example and comparative example were observed using an optical microscope, and the minimum exposure amount (mJ / cm²) required to form a cured product without peeling was determined using an optical microscope. 2 The opening width of the striped pattern with a mask opening width of 10 μm is evaluated according to the following criteria. The smaller the absolute value of the difference between the mask design value and the opening width of the cured film, the smaller the mask deviation, and the better the evaluation.

[0125] A: Mask deviation is less than 1.0μm.

[0126] B: Mask deviation is greater than 1.0μm and less than 2.0μm.

[0127] C: Mask deviation is greater than 2.0μm and less than 3.0μm.

[0128] D: Mask deviation is greater than 3.0μm.

[0129] (6) Evaluation of cross-sectional shape The minimum exposure amount (mJ / cm²) required to form a solidified product without peeling was observed using a scanning electron microscope (SEM) of the cured products obtained from each example and comparative example. 2The cross-sectional shape of a striped pattern with a mask opening width of 10 μm is determined. Patterns with a cone angle of 20° to 50° are considered to have a good cross-sectional shape, while those with a cone angle less than 20° or greater than 50° are considered to have a poor cross-sectional shape.

[0130] (7) Evaluation of light-blocking properties For the OD value of the cured product of the photosensitive composition obtained from each embodiment and comparative example at the minimum exposure amount at which a pattern can be formed, the intensity of the incident light and the transmitted light were measured using an X-rite 361T (visual) densitometer and calculated by the following formula.

[0131] OD value = log 10 (I0 / I) I0: Incident light intensity I: Transmitted light intensity In addition, the film thickness (μm) of the cured material was measured using a contact-type film thickness meter DEKTAK150 (manufactured by ULVAC Co., Ltd.), and the OD value / film thickness was calculated. Thus, the light-shielding property of each cured material per 1 μm was evaluated.

[0132] (8) Evaluation of the luminescence of organic EL display devices A schematic diagram illustrating the fabrication steps of the organic EL display device using the photosensitive compositions obtained in the various embodiments and comparative examples is shown below. Figure 3First, a 10 nm ITO transparent conductive film was formed on the entire surface of a 38 mm × 46 mm alkali-free glass substrate 1 using sputtering, and etched to form the first electrode (transparent electrode) 2. Simultaneously, an auxiliary electrode 3 for removing the second electrode was also formed. The substrate 1 was ultrasonically cleaned for 10 minutes using Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.), followed by rinsing with ultrapure water. Next, a photosensitive composition (NB-1) was spin-coated onto the entire surface of the substrate 1 and pre-baked on a heated plate at 110°C for 2 minutes. This pre-baked film was then exposed to the minimum exposure of each photosensitive composition using a high-pressure mercury lamp as the light source, through a photomask. It was then developed using a 2.38% (w / w) TMAH aqueous solution to dissolve unwanted portions and rinsed with pure water. The resulting resin pattern was then heat-treated at 230°C for 60 minutes in a hot air oven. As described above, an insulating layer 4 is formed within the effective area of ​​the substrate 1, with openings 70 μm wide and 260 μm long, spaced at 155 μm intervals in the width direction and 465 μm intervals in the length direction, each opening exposing the first electrode 2. As described above, an insulating layer 4 with an opening ratio of 25% is formed within the effective area of ​​the substrate, which is a quadrilateral with a side length of 16 mm. The thickness of the insulating layer 4 is approximately 1.0 μm.

[0133] Next, nitrogen plasma treatment is performed as a pretreatment, followed by the formation of an organic EL layer 5 containing the light-emitting layer using vacuum evaporation. It should be noted that the vacuum level during evaporation is 1 × 10⁻⁶. -3 Below Pa, during evaporation, substrate 1 is rotated relative to the evaporation source. First, a 10 nm thick compound (HT-1) is deposited as a hole injection layer, and a 50 nm thick compound (HT-2) is deposited as a hole transport layer. Next, on the light-emitting layer, a compound (GH-1) as the host material and a compound (GD-1) as the dopant material are deposited to a thickness of 40 nm, with a doping concentration of 10%. Next, as the electron transport material, compound (ET-1) and compound (LiQ) are stacked at a 1:1 volume ratio to a thickness of 40 nm. The structure of the compounds used in the organic EL layer is shown below.

[0134] [Chemical Formula 9] Next, after depositing a 2nm layer of compound (LiQ), Mg and Ag were deposited at a volume ratio of 10:1 for 10nm to form the second electrode (non-transparent electrode) 6. Finally, a cover glass plate was bonded to the substrate using an epoxy resin adhesive under a low-humidity nitrogen atmosphere to seal the surface, thus fabricating four top-emitting organic EL display devices with one 5mm side quadrilateral on a single substrate. It should be noted that the film thickness referred to here is the value displayed by a quartz oscillating film thickness monitor.

[0135] The four organic EL display devices were made to emit light, and the emitting surfaces were observed using an optical microscope. The presence or absence of non-illuminated units was evaluated according to the following criteria.

[0136] A: All four organic EL display devices have no non-illuminated units.

[0137] B: In 4 organic EL display devices, 1 has a non-illuminated unit.

[0138] C: Of the four organic EL display devices, two have non-illuminated units.

[0139] D: Of the four organic EL display devices, three have non-illuminated units.

[0140] (9) Evaluation of minute residues For the developing films obtained from the various embodiments and comparative examples with a pre-baking temperature of 120°C, the lowest exposure amount (mJ / cm²) that could be formed without peeling was observed using a scanning electron microscope (SEM). 2 The presence or absence of minute residues was determined from 20 randomly selected openings within a 10 μm striped pattern. The number of minute residues smaller than 0.1 μm within each opening was measured, and the average of the 20 locations was taken as the number of minute residues. Evaluation was based on the following criteria: A to C were considered acceptable, while D and E were considered unacceptable.

[0141] A: The number of minute residues is more than 0 and less than 1. B: More than 1 but less than 10 tiny residues C: More than 10 but less than 20 tiny residues D: The number of tiny residues is more than 20 but less than 30. E: There are more than 30 tiny residues.

[0142] <Manufacturing Example> (Synthesis Example 1: Copolymer (a-1)) Separately, 17.13 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd., "PQMA"; hereinafter referred to as PQMA), 3.31 g of methacrylic acid (hereinafter referred to as MAA), and 19.56 g of stearyl methacrylate were completely dissolved in 100.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and 3.66 g of V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation), used as a polymerization initiator, were completely dissolved in 15.0 g of PGMEA. The two solutions were simultaneously added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C under a nitrogen atmosphere in a 300 mL three-necked flask. After the addition was complete, the reaction was carried out at 85°C to obtain a 20% by mass solution of the solid component of the copolymer of PQMA / MAA / stearyl methacrylate = 50 / 20 / 30 (mol%). Various copolymers were prepared by changing the reaction time of the copolymer, and a copolymer with a weight average molecular weight of 8400 was prepared into a 20% by mass solution of the solid component of copolymer (a-1).

[0143] (Synthesis Example 2: Copolymer (a-2)) Using the same method as in Synthesis Example 1, 2-allylphenol was used instead of PQMA for the monomers added. The amount of 2-allylphenol was set to 14.43 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 3.70 g and 21.87 g, respectively, thus obtaining a 20% by mass solid solution of a copolymer of 2-allylphenol / MAA / stearyl methacrylate = 50 / 20 / 30 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-2) was prepared from a copolymer with a weight average molecular weight of 8500.

[0144] (Synthesis Example 3: Copolymer (a-3)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 10.73 g, and the amounts of 2-allylphenol (5.39 g), MAA (3.45 g), and stearyl methacrylate (20.42 g) were also set, thus obtaining a 20% by mass solid solution of the copolymer of PQMA / 2-allylphenol / MAA / stearyl methacrylate = 30 / 20 / 20 / 30 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-3) was prepared from the copolymer with a weight average molecular weight of 8500.

[0145] (Synthesis Example 4: Copolymer (a-4)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 14.34 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 20.46 g, thereby obtaining a 20% by mass solid solution of a copolymer of PQMA / MAA / stearyl methacrylate = 40 / 30 / 30 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-4) was prepared from a copolymer with a weight average molecular weight of 8300.

[0146] (Synthesis Example 5: Copolymer (a-5)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 25.81 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 5.36 g, thereby obtaining a 20% by mass solid solution of the copolymer with a PQMA / MAA / stearyl methacrylate ratio of 55 / 39 / 6 (mol%). Various copolymers were prepared by changing the reaction time, and a copolymer with a weight-average molecular weight of 8700 was prepared into a 20% by mass solid solution of copolymer (a-5).

[0147] (Synthesis Example 6: Copolymer (a-6)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 16.66 g, and the amounts of MAA, 0.88 g, and stearyl methacrylate, 22.47 g, were used to obtain a 20% by mass solid solution of the copolymer with a PQMA / MAA / stearyl methacrylate ratio of 55 / 6 / 39 (mol%). Various copolymers were prepared by varying the reaction time, and a copolymer with a weight-average molecular weight of 8400 was prepared as a 20% by mass solid solution of copolymer (a-6).

[0148] (Synthesis Example 7: Copolymer (a-7)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 31.70 g, and the amounts of MAA, stearyl methacrylate, and ortho-stearyl methacrylate were set to 1.68 g and 6.62 g, respectively, thus obtaining a 20% by mass solution of the solid component of a copolymer with a PQMA / MAA / stearyl methacrylate ratio of 82 / 9 / 9 (mol%). Various copolymers were prepared by varying the reaction time of this copolymer, and a 20% by mass solution of the solid component of copolymer (a-7) was prepared from a copolymer with a weight average molecular weight of 8200.

[0149] (Synthesis Example 8: Copolymer (a-8)) Separately, 13.29 g of PQMA, 5.61 g of MAA, and 15.8 g of stearyl methacrylate were completely dissolved in 100.0 g of PGMEA, and 3.66 g of V-601, acting as a polymerization initiator, was completely dissolved in 15.0 g of PGMEA. The two solutions were simultaneously added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C under a nitrogen atmosphere in a 300 mL three-necked flask for copolymerization. Then, the reaction vessel was purged with air, and 5.30 g of glycidyl methacrylate (hereinafter referred to as GMA) was added dropwise over 1 hour using a drop pump to initiate the addition reaction. The vessel was further stirred to obtain a 20% by mass solution of the solid component of the copolymer of PQMA / MAA / stearyl methacrylate / GMA addition MAA = 40 / 15 / 25 / 20 (mol%). By changing the reaction time of the copolymer, various types were produced, and a copolymer with a weight-average molecular weight of 8500 was made into a 20% by mass solution of the solid component of copolymer (a-8).

[0150] (Synthesis Example 9: Copolymer (a-9)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 17.13 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 19.56 g, thereby obtaining a 20% by mass solid solution of the copolymer of PQMA / MAA / stearyl methacrylate = 50 / 20 / 30 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-9) was prepared from a copolymer with a weight average molecular weight of 21000.

[0151] (Synthesis Example 10: Copolymer (a-10)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 17.13 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 19.56 g, thereby obtaining a 20% by mass solid solution of the copolymer of PQMA / MAA / stearyl methacrylate = 50 / 20 / 30 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-10) was prepared from the copolymer with a weight average molecular weight of 63000.

[0152] (Synthesis Example 11: Copolymer (a-11)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 18.47 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 19.46 g, thereby obtaining a 20% by mass solution of the solid component of a copolymer of PQMA / MAA / stearyl methacrylate = 56 / 13 / 31 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solution of the solid component of copolymer (a-11) was prepared from a copolymer with a weight average molecular weight of 14300.

[0153] (Synthesis Example 12: Copolymer (a-12)) Using the same method as in Synthesis Example 1, isodecyl methacrylate was used instead of stearyl methacrylate for the monomers added. The amount of PQMA added was set to 22.03 g, MAA to 2.47 g, and isodecyl methacrylate to 15.50 g, thereby obtaining a 20% by mass solid solution of a copolymer of PQMA / MAA / isodecyl methacrylate = 56 / 13 / 31 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-12) was prepared from a copolymer with a weight average molecular weight of 14500.

[0154] (Synthesis Example 13: Copolymer (a-13)) Using the same method as in Synthesis Example 1, but replacing stearyl methacrylate with 2-EHMA, the amount of PQMA added was set to 23.15 g, MAA to 2.59 g, and 2-EHMA to 14.26 g, thus obtaining a 20% by mass solid solution of a copolymer with PQMA / MAA / 2-EHMA = 56 / 13 / 31 (mol%). Various copolymers were prepared by varying the reaction time, and a 20% by mass solid solution of copolymer (a-13) was prepared from a copolymer with a weight-average molecular weight of 14800.

[0155] (Synthesis Example 14: Copolymer (a-14)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 6.93 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 6.69 g and 26.38 g, respectively, thus obtaining a 20% by mass solid solution of the copolymer of PQMA / MAA / stearyl methacrylate = 20 / 40 / 40 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-14) was prepared from a copolymer with a weight average molecular weight of 8500.

[0156] (Synthesis Example 15: Copolymer (a-15)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 7.62 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 31.89 g, thereby obtaining a 20% by mass solid solution of the copolymer with PQMA / MAA / stearyl methacrylate = 30 / 4 / 66 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-15) was prepared from a copolymer with a weight average molecular weight of 8300.

[0157] (Synthesis Example 16: Copolymer (a-16)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 17.28 g, and the amounts of MAA, stearyl methacrylate, and ortho-stearyl methacrylate were set to 18.34 g and 4.38 g, respectively, thus obtaining a 20% by mass solid solution of a copolymer with a PQMA / MAA / stearyl methacrylate ratio of 30 / 66 / 4 (mol%). Various copolymers were prepared by varying the reaction time, and a copolymer with a weight-average molecular weight of 8600 was prepared into a 20% by mass solid solution of copolymer (a-16).

[0158] (Synthesis Example 17: Copolymer (a-17)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 26.25 g, and the amounts of MAA, MAA, and stearyl methacrylate were set to 4.54 g, thereby obtaining a 20% by mass solid solution of a copolymer with PQMA / MAA / stearyl methacrylate = 55 / 40 / 5 (mol%). Various copolymers were prepared by changing the reaction time, and a copolymer with a weight average molecular weight of 8300 was prepared into a 20% by mass solid solution of copolymer (a-17).

[0159] (Synthesis Example 18: Copolymer (a-18)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 16.48 g, and the amounts of MAA, 0.72 g, and stearyl methacrylate (t-methacrylate) to 22.80 g were also set, thereby obtaining a 20% by mass solid solution of the copolymer with a PQMA / MAA / t-methacrylate ratio of 55 / 5 / 40 (mol%). Various copolymers were prepared by varying the reaction time, and a copolymer with a weight-average molecular weight of 8700 was prepared as a 20% by mass solid solution of copolymer (a-18).

[0160] (Synthesis Example 19: Copolymer (a-19)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 33.93 g, and the amounts of MAA, stearyl methacrylate, and ortho-stearyl methacrylate were set to 5.14 g, thereby obtaining a 20% by mass solid solution of the copolymer with a PQMA / MAA / stearyl methacrylate ratio of 88 / 5 / 7 (mol%). Various copolymers were prepared by varying the reaction time, and a copolymer with a weight-average molecular weight of 8300 was prepared into a 20% by mass solid solution of copolymer (a-19).

[0161] (Synthesis Example 20: Copolymer (a-20)) Using the same method as in Synthesis Example 8, the amount of PQMA added was set to 10.26 g, MAA to 9.08 g, and stearyl methacrylate to 9.76 g. The amount of GMA involved in the addition reaction was set to 10.91 g, thereby obtaining a 20% by mass solution of the solid component of a copolymer of PQMA / MAA / stearyl methacrylate / GMA addition MAA = 30 / 15 / 15 / 40 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer. A copolymer with a weight average molecular weight of 8200 was prepared into a 20% by mass solution of the solid component of copolymer (a-20).

[0162] (Synthesis Example 21: Copolymer (a-21)) Using the same method as in Synthesis Example 8, the amount of MAA added was set to 9.27 g, the amount of stearyl methacrylate was set to 24.35 g, and the amount of GMA involved in the addition reaction was set to 6.38 g, thereby obtaining a 20% by mass solid solution of a copolymer of MAA / stearyl methacrylate / GMA addition MAA = 35 / 40 / 25 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solid solution of copolymer (a-21) was prepared from a copolymer with a weight average molecular weight of 8400.

[0163] (Synthesis Example 22: Copolymer (a-22)) Using the same method as in Synthesis Example 1, the amount of PQMA added was set to 26.12 g, and the amount of GMA was set to 13.88 g, thereby obtaining a 20% by mass solution of the solid component of the copolymer with PQMA / GMA = 60 / 40 (mol%). Various copolymers were prepared by changing the reaction time of this copolymer, and a 20% by mass solution of the solid component of copolymer (a-22) was prepared from a copolymer with a weight average molecular weight of 8600.

[0164] (Synthetic Example 23: Dispersion resin with tertiary amino, carboxyl and olefinic unsaturated groups (f-1)) 400.0g of PGMEA was added to a pressure vessel equipped with a stirrer, thermometer, reflux condenser, and dropping pump. The reaction vessel was filled with nitrogen, and the temperature was raised to 90°C. Using the dropping pump, a mixture of 2.0g of 2-dimethylaminoethyl methacrylate, 31.0g of methyl methacrylate, 20.0g of 2-ethylhexyl methacrylate, 30.0g of styrene, 17.0g of methacrylic acid, 2.0g of azobisisobutyronitrile (as polymerization initiator), and 3.0g of n-dodecyl mercaptan was added dropwise over 3 hours to copolymerize the mixture. Then, the reaction vessel was purged with air, and 10.0g of GMA was added dropwise over 1 hour to initiate an addition reaction. The mixture was then stirred for another 2 hours. The result was a dispersion resin (f-1) solution with tertiary amino, carboxyl and olefinic unsaturated groups, having a base value of 11 mmol / 100g, an acid value of 73 mg KOH / g, a weight-average molecular weight of 7000, and a solid component concentration of 20% by mass.

[0165] (Synthesis Example 24: Fluorene Acrylate Solution (e-1)) 400.00 g of methyl isobutyl ketone as a solvent was added to a flask, along with 350.00 g of 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene, 112.10 g of acrylic acid, 1.50 g of p-hydroxyanisole as a polymerization inhibitor, and 0.30 g of tetraethylammonium bromide as a catalyst. The liquid temperature was maintained at 140 °C, and the mixture was stirred for 5 hours to allow the reaction to proceed. Heating was then stopped, and the mixture was cooled to room temperature. The reactants were washed with water by separation and then dried under reduced pressure to obtain fluorene acrylate (mol% ratio of compound represented by formula (6): mol% of compound represented by formula (7) = 73:27). Next, PGMEA was added at a solid content of 30% by mass, and the mixture was stirred to obtain a fluorene acrylate solution (e-1).

[0166] [Chemical Formula 10] (Synthesis Example 25: Copolymer (a-23)) Separately, 13.02 g of PQMA, 4.87 g of MAA, and 17.96 g of stearyl methacrylate were completely dissolved in 100.0 g of PGMEA, and 3.66 g of V-601 (as a polymerization initiator) was completely dissolved in 15.0 g of PGMEA. The two solutions were simultaneously added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C under a nitrogen atmosphere in a 300 mL three-necked flask for copolymerization. Then, the reaction vessel was purged with air, and 4.15 g of GMA was added dropwise over 1 hour using a drop pump to initiate the addition reaction. The vessel was further stirred to obtain a 20% by mass solution of the solid component of the copolymer of PQMA / MAA / stearyl methacrylate / GMA addition MAA = 40 / 15 / 29 / 16 (mol%). By changing the reaction time of the copolymer, various types were prepared, and a copolymer with a weight average molecular weight of 8500 was made into a 20% by mass solution of the solid component of copolymer (a-23).

[0167] (Synthesis Example 26: Copolymer (a-24)) Separately, 13.33 g of PQMA, 3.52 g of MAA, and 21.13 g of stearyl methacrylate were completely dissolved in 100.0 g of PGMEA, and 3.66 g of V-601 (as a polymerization initiator) was completely dissolved in 15.0 g of PGMEA. The two solutions were simultaneously added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C under a nitrogen atmosphere in a 300 mL three-necked flask for copolymerization. Then, the reaction vessel was purged with air, and 2.02 g of GMA was added dropwise over 1 hour using a drop pump to initiate the addition reaction. The vessel was further stirred to obtain a 20% by mass solution of the solid component of the copolymer of PQMA / MAA / stearyl methacrylate / GMA addition MAA = 42 / 15 / 35 / 8 (mol%). By changing the reaction time of the copolymer, various types were prepared, and a copolymer with a weight average molecular weight of 8500 was made into a 20% by mass solution of the solid component of copolymer (a-24).

[0168] (Synthesis Example 27: Copolymer (a-25)) Separately, 13.89 g of PQMA, 2.89 g of MAA, and 22.21 g of stearyl methacrylate were completely dissolved in 100.0 g of PGMEA, and 3.66 g of V-601 (as a polymerization initiator) was completely dissolved in 15.0 g of PGMEA. The two solutions were simultaneously added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C under a nitrogen atmosphere in a 300 mL three-necked flask for copolymerization. Then, the reaction vessel was purged with air, and 1.01 g of GMA was added dropwise over 1 hour using a drop pump to initiate the addition reaction. The vessel was further stirred to obtain a 20% by mass solution of the solid component of the copolymer of PQMA / MAA / stearyl methacrylate / GMA addition MAA = 44 / 15 / 37 / 4 (mol%). By changing the reaction time of the copolymer, various types were produced, and a copolymer with a weight average molecular weight of 8500 was made into a 20% by mass solution of the solid component of copolymer (a-25).

[0169] (Example 1: Manufacturing of Pigment Dispersion (B-1)) 525 g of Irgaphor Black S0100CF (manufactured by BASF) as pigment, 675 g of a 20% by mass PGMEA solution of a dispersion resin (f-1) having tertiary amino, carboxyl, and olefinic unsaturated groups, 90 g of a dispersant with an amine value of 20 mg KOH / g as described in Synthesis Example 2 of Japanese Patent Application Publication No. 2020-070352, and 1710 g of PGMEA were added to a container and stirred for 20 minutes using a homogenizer to obtain a pre-dispersion. The solution was then poured into a container filled with 70% by volume 0.10 mm... The pre-dispersed liquid obtained was supplied to the Ultra Apex Mill centrifugal separator manufactured by Hiroshima Metal & Machinery Co., Ltd. and dispersed at a rotation speed of 10 m / s for 3 hours to obtain a pigment dispersion (B-1) with a solid component concentration of 25% by mass.

[0170] (Example 2: Manufacturing of pigment dispersion (B-2)) 11.49 g of Irgaphor Black S0100CF (manufactured by BASF) as pigment, 2.77 g of the dispersant (100% solid component) described in Patent Document 2 <Dispersant-I>, 14.37 g of the alkali-soluble resin (40% PGMEA solution solid component) described in Patent Document 2 <Synthesis Example 1>, 55.40 g of PGMEA, and 15.98 g of MB were added to a container, and the mixture was dispersed for 3 hours at 25-45°C using a paint shaker. 0.5 mm beads were used. Zirconia beads were added at a mass ratio of 2.5 times that of the dispersion. After dispersion, the beads were separated from the dispersion using a filter to obtain a pigment dispersion (B-2) with a solid component concentration of 20% by mass.

[0171] (Example 1) To a 20.60 g pigment dispersion (B-1), 28.43 g of a 20% by mass PGMEA solution of copolymer (a-1), 0.88 g of ADEKA ARKLS (registered trademark) NCI-831 as a photopolymerization initiator, 3.26 g of KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.) as a free radical polymerizable compound, 0.02 g of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie Co., Ltd.), and 46.81 g of PGMEA were added to obtain a negative photosensitive composition (NB-1) with a total solid component concentration of 15% by mass. A cured negative photosensitive composition and an organic EL display device comprising the cured composition were further prepared according to the aforementioned method.

[0172] (Examples 2-13) Using the same method as in Example 1, copolymers (a) (a-2) to (a-13) were used as inputs to obtain negative photosensitive compositions (NB-2) to (NB-13) and their cured products, as well as organic EL display devices having the cured products.

[0173] (Example 14) To a 25.70 g pigment dispersion (B-1), 22.00 g of a 20% PGMEA solution of copolymer (a-13), 1.00 g of ADEKA ARKLS (registered trademark) NCI-831 as a photopolymerization initiator, 3.16 g of KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.) as a free radical polymerizable compound, 0.02 g of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie Co., Ltd.), and 48.13 g of PGMEA were added to obtain a negative photosensitive composition (NB-14) with a total solid component concentration of 15% by mass. A cured negative photosensitive composition and an organic EL display device comprising the cured composition were further prepared according to the aforementioned method.

[0174] (Example 15) To a 25.70 g pigment dispersion (B-1), 22.00 g of a 20% PGMEA solution of copolymer (a-13), 1.00 g of ADEKA ARKLS (registered trademark) NCI-831 as a photopolymerization initiator, 1.58 g of KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.) as a free radical polymerizable compound, 5.26 g of fluorene acrylate solution (e-1), 0.02 g of organosilicon surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie Co., Ltd.), and 48.13 g of PGMEA were added to obtain a negative photosensitive composition (NB-15) with a total solid component concentration of 15% by mass. A cured negative photosensitive composition and an organic EL display device comprising the cured composition were further prepared according to the aforementioned method.

[0175] (Examples 16-18) Using the same method as in Example 1, copolymers (a) (a-23) to (a-25) were used as inputs to obtain negative photosensitive compositions (NB-26) to (NB-28) and their cured products, as well as organic EL display devices having the cured products.

[0176] (Example 19) To 20.60 g of pigment dispersion (B-1), 27.85 g of a 20% by mass PGMEA solution of copolymer (a-25), 0.87 g of ADEKA ARKLS (registered trademark) NCI-831 (manufactured by ADEKA Co., Ltd.) as a photopolymerization initiator, 3.24 g of KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.) as a free radical polymerizable compound, 0.15 g of ADEKA APluronic (registered trademark) 17R-2 (manufactured by ADEKA Co., Ltd.) as a residue inhibitor, 0.02 g of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie Co., Ltd.), and 46.81 g of PGMEA were added to obtain a negative photosensitive composition (NB-29) with a total solid component concentration of 15% by mass. A cured negative photosensitive composition and an organic EL display device comprising the cured composition were further prepared according to the aforementioned method.

[0177] (Comparative Examples 1-9) Using the same method as in Example 1, copolymers (a-14) to (a-22) were used as inputs to obtain negative photosensitive compositions (NB-16) to (NB-24) and their cured products, as well as organic EL display devices having the cured products.

[0178] (Comparative Example 10) 14.93 g of acrylic soluble resin-IV (40% PGMEA solution of solid component) described in <Synthesis Example 3> of Patent Document 2, 0.76 g of photopolymerization initiator-I described in <Synthesis Example 4> of Patent Document 2, 1.16 g of KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) as a free radical polymerizable compound, 1.16 g of LIGHT ACRYLATE TMP-A (manufactured by Kyoeisha Chemical Co., Ltd.), 0.02 g of surfactant "BYK" 330 (manufactured by BYK-Chemie Co., Ltd.), 24.06 g of PGMEA, and 8.25 g of MB were added to 49.65 g of pigment dispersion (B-2) to obtain a negative photosensitive composition (NB-25) with a total solid component concentration of 19% by mass. A cured negative photosensitive composition and an organic EL display device having the cured composition were further prepared according to the aforementioned method.

[0179] The composition of the copolymer (a) used in each embodiment and comparative example is shown in Tables 1, 2 and 3, and the evaluation results are shown in Tables 4, 5 and 6.

[0180] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] Based on the above results, the negative photosensitive compositions of the examples exhibit smaller mask deviations during fine pattern processing compared to the negative photosensitive compositions of the comparative examples. Furthermore, they demonstrate excellent solubility in alkaline developing solutions, suppress the formation of developing residues over a wide range of pre-baking temperatures, and produce excellent cone shapes in the cured products. Consequently, organic EL display devices using these cured products exhibit excellent luminescence properties. Even in Examples 14 and 15, which exhibit high opacity (OD value of 1.3 per 1.0 μm thickness of the cured product), excellent solubility in alkaline developing solutions is achieved through the use of copolymer (a). In particular, in Example 15, the use of the free radical polymerizable compound (e-1) reduces the cone angle after development, resulting in a good cone angle after curing and excellent luminescence properties. Additionally, in Examples 16, 17, and 19, the pre-baking temperature tolerance is maintained, and minute residues smaller than 0.1 μm are suppressed.

[0181] Explanation of reference numerals in the attached figures 1: Alkali-free glass substrate 2: First electrode (transparent electrode) 3: Auxiliary electrode 4: Insulation layer 5: Organic EL layer 6: Second electrode (non-transparent electrode) θ: Cone angle

Claims

1. A copolymer which is a copolymer (a) containing structural units represented by the following formulae: a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (3), and a structural unit represented by formula (4), the structural unit represented by formula (1) and the structural unit represented by formula (2) are contained in a total amount of 70 to 100 mol% in 100 mol% of the total of all structural units of the copolymer (a), the structural unit represented by formula (3), and the structural unit represented by formula (4), the structural unit represented by any one of formulae (1) to (4) is contained in a total amount of 70 to 100 mol% in 100 mol% of the total of all structural units of the copolymer (a), when the total number of moles of the structural unit represented by formula (1) and the structural unit represented by formula (2) is X, the number of moles of the structural unit represented by formula (3) is Y, and the number of moles of the structural unit represented by formula (4) is Z, in the copolymer (a), a value A obtained by dividing X by Y is 1.0 to 10.0, and a value B obtained by dividing X by Z is 1.0 to 10.0, [Chemical Formula 1] In formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents a single bond or an alkylene group having 1 to 3 carbon atoms; n 1 is an integer, and represents 1 or 2; R 3 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; n 2 is an integer, and represents 0 to 2; represents a bonding site; In formula (2), R 4 represents a hydrogen atom or a methyl group; R 5 represents an alkylene group having 1 to 3 carbon atoms; n 3 is an integer, and represents 1 or 2; R 6 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; n 4 is an integer, and represents 0 to 2; represents a bonding site; In formula (3), R 7 represents a hydrogen atom or a methyl group; represents a bonding site; In formula (4), R 8 represents a hydrogen atom or a methyl group; R 9 represents an alkyl group having 5 to 18 carbon atoms; represents a bonding site.

2. The copolymer according to claim 1, having a weight average molecular weight (Mw) of 10,000 to 50,000.

3. The copolymer of claim 1 or 2, wherein, the copolymer (a) has the structural unit represented by formula (1).

4. The copolymer of claim 1 or 2, wherein, R in the formula (4) is a branched alkyl group having 7 to 15 carbon atoms. 9 R in the formula (4) is a branched alkyl group having 7 to 15 carbon atoms.

5. The copolymer of claim 1 or 2, wherein, the copolymer (a) has a structural unit represented by formula (8), [Chemical Formula 2] In formula (8), R 14 and R 15 each independently represents a hydrogen atom or a methyl group, R 16 represents a divalent group having a hydroxyl group with 4 to 12 carbon atoms.

6. The copolymer of claim 5, wherein, the copolymer (a) contains 5 to 18 mol% of the structural unit represented by formula (8) in 100 mol% of the total of all structural units of the copolymer (a).

7. A photosensitive composition containing, in addition to the copolymer (a) according to claim 1 or 2, a pigment, a photosensitizer, and an organic solvent.

8. The photosensitive composition according to claim 7, further containing a (meth)acrylate compound having two 9,9-bis(naphthyl)fluorene skeletons in a molecule and two ethylenically unsaturated double bond groups in a molecule, and having a negative-type photosensitivity.

9. The photosensitive composition according to claim 7, further containing a compound represented by formula (9), and having a negative-type photosensitivity, [Chemical Formula 3] in formula (9), PO represents an oxypropylene group, EO represents an oxyethylene group, x, y, and z each independently represent an integer of 1 to 50, and satisfy a relationship of y < x + z.

10. A cured product obtained by curing the photosensitive composition according to claim 7.

11. An organic EL display device provided with the cured product according to claim 10.

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