Compounds, resin compositions, cured products, and display devices

Abstract

The purpose of the present invention is to provide: a resin composition achieving a high residual film rate when alkaline development is performed; and a compound employed therein.　In order to achieve the aforementioned purpose, the compound of the present invention takes the form represented by formula (1). (In the formula, An- represents an anion that has a specific structure and that has n valency. R1-R4 each independently represent an alkyl group having 5-10 carbon atoms. n represents an integer from 1 to 3.)

Description

[Technical Field]

[0001] The present invention relates to a compound, a resin composition, a cured product using the same, and a display device. [Background technology]

[0002] Cured products obtained by curing compositions containing polyimide or polybenzoxazole are widely used as insulating films, protective films, and planarization films for semiconductor elements and display devices. When used in display devices, for example, in applications such as the pixel division layer of organic electroluminescence (EL) displays and the black matrix of liquid crystal displays, it is required to lower the light transmittance of the cured product in order to improve contrast. Furthermore, to prevent degradation, malfunction, and leakage current caused by light entering the thin-film transistors (TFTs) used to drive the display device, it is also required to lower the transmittance of the pixel division layer of organic EL displays and the planarization film provided on the TFT substrate of organic EL displays.

[0003] Techniques for reducing the light transmittance in the visible light region above 400 nm in cured products include adding colorants such as carbon black, organic or inorganic pigments, or dyes to the resin composition, as seen in black matrix materials and RGB paste materials for liquid crystal displays.

[0004] Techniques for reducing the light transmittance of cured resin compositions include, for example, adding a quinone diazide compound, a dye soluble in both alkaline developer and organic solvent to an alkali-soluble resin (see Patent Document 1), adding a black oil-soluble dye to a photosensitive resin (see Patent Document 2), adding an esterified quinone diazide compound and at least one colorant selected from dyes, inorganic pigments, and organic pigments to an alkali-soluble heat-resistant resin (see Patent Document 3), and adding a xanthene-based acid dye and a triarylmethane-based acid dye to a binder resin (see Patent Document 4). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 7-261015 [Patent Document 2] Japanese Patent Application Publication No. 10-254129 [Patent Document 3] Japanese Patent Publication No. 2004-145320 [Patent Document 4] Japanese Patent Publication No. 2013-50707 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, these techniques had a drawback: the use of dyes resulted in significant film loss during alkaline development, leading to a low residual film rate. [Means for solving the problem]

[0007] The present invention has the following configuration. [1] A compound represented by formula (1).

[0008] [ka]

[0009] (In formula (1), A n- R is an n-valent anion represented by formula (2) or formula (3). 1 ~R 4 Each of these is an alkyl group having 5 to 10 carbon atoms. n is an integer between 1 and 3.

[0010] [ka]

[0011] (In formula (2), R 5 ~R8 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R 9 ~R 14 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. R 15 ~R 18 each independently represents a hydrogen atom, a halogen atom, -SO3H, -SO3 - , -SO3NR 19 R 20 , -COOH, -COO - , -COOR 21 , -CONR 22 R 23 , -OR 24 , -NR 25 R 26 or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R 19 ~R 26 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R 5 ~R 8 and R 15 ~R 18 among them, at least one is a monovalent hydrocarbon group having 1 to 10 carbon atoms having -SO3 - or -COO - , -SO3 - or -COO - . X represents -SO3 - or -COO - .)

[0012]

Chemical formula

[0013] (In formula (3), R 27 [[_ID=67]]~R 30 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R 31 ~R 36 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. R 37 ~R 41These are, independently, a hydrogen atom, a halogen atom, -SO3H, and -SO3. - , -SO3NR 42 R 43 -COOH, -COO - ,-COOR 44 ,-CONR 45 R 46 , -OR 47 , -NR 48 R 49 Alternatively, it represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. 37 ~R 41 Among these, adjacent elements may be joined to each other, forming a ring structure. 42 ~R 49 Each of these independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrogen atom or substituents. 27 ~R 30 and R 37 ~R 41 Of these, at least two are -SO3 - Or -COO - A monovalent hydrocarbon group having 1 to 20 carbon atoms, -SO3 - or -COO - (That is the case.) [2] In equation (1), R 1 , R 2 , R 3 and R 4 The compound described in [1] above, wherein all substituents are identical. [3] R in equation (1) 1 , R 2 , R 3 and R 4 The compound according to [1] or [2] above, wherein all of them are alkyl groups having 5 or 6 carbon atoms. [4] A compound according to any of [1] to [3] above, wherein the maximum absorption wavelength in the region between 350 nm and 700 nm is located in any of the regions between 500 nm and 700 nm. [5] A resin composition comprising any of the compounds described in [1] to [4] above, and (A) an alkali-soluble resin. [6] The resin composition according to [5], wherein the proportion of the mass of the ammonium cation species in formula (1) to the total mass of organic cation species in the resin composition is 50% by mass or more and 100% by mass or less. [7] A compound described in any of the above [1] to [4], A compound having a maximum absorption wavelength in the range of 500 nm to less than 580 nm in the region of 350 nm to 700 nm, The resin composition according to claim 5 or 6, comprising a compound having a maximum absorption wavelength in the range of 580 nm to 700 nm in the region of 350 nm to 700 nm. [8] The resin composition according to any one of [5] to [7] above, wherein the total mass of all chlorine atoms and all bromine atoms contained in the resin composition is 150 ppm by mass or less with respect to the total mass of solids in the resin composition. [9] Furthermore, the resin composition according to any one of [5] to [8] above, comprising (B) a photosensitive compound.

[10] The resin composition according to [9] above, wherein the (B) photosensitive compound contains a quinone diazide compound.

[11] The resin composition according to

[10] , wherein the quinone diazide compound contains a compound in which the sulfonic acid of the quinone diazide is ester-bonded to the hydroxyl group of the polyhydroxy compound, and the proportion of hydroxyl groups ester-bonded to the sulfonic acid of the quinone diazide is 50 mol% or more and 90 mol% or less of the total hydroxyl groups.

[12] Furthermore, the resin composition according to any one of [5] to

[11] above, comprising (C) a thermochromic compound.

[13] The resin composition according to

[12] , wherein the (C) thermochromic compound contains a compound that, upon heating at 120°C or higher, produces a maximum absorption wavelength in any of the regions between 350 nm and 500 nm in the region between 350 nm and 700 nm.

[14] The resin composition according to

[12] or

[13] , wherein the (C) thermochromic compound contains an aromatic hydrocarbon compound having at least one aromatic CH bond and at least three phenolic hydroxyl groups in one aromatic ring, and further contains a triazine ring-containing compound represented by formula (4).

[0014] [ka]

[0015] (In formula (4), R 50 ~R 55 Each of these independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkenyl ether group with 2 to 10 carbon atoms, a methylol group, and an alkoxymethyl group. However, R 50 ~R 55 (At least one of these is a methylol group or an alkoxymethyl group.)

[15] The resin composition according to any one of [5] to

[14] above, wherein the alkali-soluble resin (A) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and copolymers thereof.

[16] A resin composition according to any one of [5] to

[15] above, used for forming a pixel splitting layer of an organic EL display device.

[17] A cured product obtained by curing any of the resin compositions described in [5] to

[16] above.

[18] A cured product containing any of the compounds described in [1] to [4] above.

[19] A display device comprising the cured material described in

[17] or

[18] above. [Effects of the Invention]

[0016] By using the compound of the present invention, a resin composition with a high residual film rate during alkaline development can be obtained. [Brief explanation of the drawing]

[0017] [Figure 1] It is a schematic diagram of a substrate used in an organic EL display device.

Embodiments for Carrying out the Invention

[0018] Hereinafter, the present invention will be described in detail.

[0019] The compound of the present invention is a compound represented by formula (1). The compound represented by formula (1) has an anion part represented by A n- and a cation part represented by (R 1 R 2 R 3 R 4 N + ). n It consists of.

[0020] In formula (1), A n- is an n-valent anion represented by the above formula (2) or formula (3).

[0021] In formula (2), R 5 to R 8 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R 9 to R 14 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. R 15 to R 18 each independently represents a hydrogen atom, a halogen atom, -SO3H, -SO3 - , -SO3NR 19 R 20 , -COOH, -COO - , -COOR 21 , -CONR 22 R 23 , -OR 24 , -NR 25 R 26 or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R 19 to R 26 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

[0022] Here, the substituents that may be present in a monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms that may have substituents include halogen atoms, hydroxyl groups, alkoxy groups, phenoxy groups, carboxyl groups, sulfo groups, acyl groups, amino groups, imino groups, amide groups, imide groups, nitro groups, cyano groups, and -SO3 - , -COO - Examples of known substituents include the following.

[0023] In formula (2), R 5 ~R 8 and R 15 ~R 18 Of these, at least one is -SO3 - Or -COO - A monovalent hydrocarbon group having 1 to 10 carbon atoms, -SO3 - or -COO - X is -SO3 - or -COO - This represents the structure represented by equation (2) when these conditions are met.

[0024] Examples of such anions include the anionic portions of xanthene-based acid dyes such as CI Acid Red 50, 52, 289; and CI Acid Violet 9, 30.

[0025] In equation (3), R 27 ~R 30 Each of these independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrogen atom or substituents. 31 ~R 36 Each of these independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. 37 ~R 41 These are, independently, a hydrogen atom, a halogen atom, -SO3H, and -SO3. - , -SO3NR 42 R 43 -COOH, -COO - ,-COOR 44 ,-CONR 45 R 46 , -OR 47, -NR 48 R 49 Alternatively, it represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. 37 ~R 41 Among these, adjacent elements may be joined to each other, forming a ring structure. 42 ~R 49 Each of these independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrogen atom or substituents.

[0026] Here, R 37 ~R 41 Among these, those adjacent to each other refer to the groups located in the ortho position of a substituent when focusing on a particular group. For example, R 38 In R 37 or R 39 However, R 38 These correspond to things that are adjacent to each other.

[0027] Here, examples of substituents that the monovalent hydrocarbon group having 1 to 20 carbon atoms may have include the substituents described above.

[0028] R 27 ~R 30 and R 37 ~R 41 Of these, at least two are -SO3 - Or -COO - A monovalent hydrocarbon group having 1 to 20 carbon atoms, -SO3 - or -COO - Therefore, satisfying this condition results in the structure represented by equation (3) becoming an anion.

[0029] Examples of such anions include the anionic portions of triarylmethane-based acid dyes such as CI Acid Violet 15, 17, 19, 21, 38, 49, 72; CI Acid Blue 1, 3, 7, 9, 15, 22, 83, 90, 93, 104, 108, 147; CI Acid Green 3, 5, 6, 8, 9, 16, 50; and CI Food Green 3.

[0030] In the cation region, R 1 ~R 4 Each of these is an alkyl group having 5 to 10 carbon atoms. That is, the cation part is a quaternary ammonium cation having four alkyl groups having 5 to 10 carbon atoms, each of which may be different. In formula (1), R 1 , R 2 , R 3 and R 4 It is preferable that all substituents are the same. That is, it is preferable that the cation portion is a quaternary ammonium cation having four identical alkyl groups with 5 to 10 carbon atoms. 1 ~R 4 If all of the substituents are the same, the reliability of an organic EL display device having a cured product made from a resin composition containing the compound of the present invention, as described later, as a pixel splitting layer can be improved. Examples of such ammonium cations having four alkyl groups with 5 to 10 carbon atoms include tetrapentylammonium cation, tetrahexylammonium cation, tetraoctylammonium cation, and tetradecylammonium cation. In particular, R in formula (1) 1 , R 2 , R 3 and R 4 Preferably, all of them are alkyl groups having 5 or 6 carbon atoms, and preferably have the structure of a tetrapentylammonium cation (5 carbon atoms) or a tetrahexylammonium cation (6 carbon atoms).

[0031] The compound represented by formula (1) can be obtained, for example, by preparing an aqueous solution of a salt containing an anion represented by formula (2) or formula (3) (hereinafter referred to as the anionic component) and an aqueous solution of a salt containing the quaternary ammonium cation (hereinafter referred to as the cationic component), and mixing the two while stirring, thereby forming the compound as a precipitate. Here, the countercation contained in the anionic component is not particularly limited, and examples include sodium cations and potassium cations. Similarly, the counteranion contained in the cationic component is not particularly limited, and examples include chloride anions and bromide anions. The compound represented by formula (1) can be obtained by recovering the formed precipitate by filtration. The obtained compound represented by formula (1) is preferably dried at about 60 to 70°C.

[0032] Compounds represented by formula (1) can be identified by known methods. For example, hydrogen nuclear magnetic resonance ( 1 The ¹H NMR spectrum is a superposition of peaks originating from the anion and cation constituting the compound. These peaks can be identified by comparing them with the ¹H NMR spectra of the anionic and cationic components separately. In particular, the triplet peak originating from the alkyl terminus (CH3) of a quaternary ammonium cation having four alkyl groups with 5 to 10 carbon atoms appears in the region of chemical shift (δ) 0.5 to 1.0. Especially when the compound represented by formula (1) has four identical alkyl groups, the peak becomes a single triplet peak, and its integral value is 12 × n.

[0033] Preferably, the compound of the present invention has a maximum absorption wavelength in the region of 350 nm to 700 nm that lies within the region of 500 nm to 700 nm. Having the maximum absorption wavelength of the compound of the present invention within this range improves the sensitivity of the photosensitive resin composition containing the compound of the present invention, as described later.

[0034] The resin composition of the present invention contains the compound of the present invention and (A) an alkali-soluble resin.

[0035] The content of the compound represented by formula (1) in the resin composition is preferably 10 to 75 parts by mass, and more preferably 20 to 50 parts by mass, per 100 parts by mass of (A) alkali-soluble resin. By having a content of 10 parts by mass or more of the compound represented by formula (1), light of the corresponding wavelength can be sufficiently absorbed. Furthermore, by having a content of 75 parts by mass or less, the amount of residue at the opening can be reduced.

[0036] In the resin composition of the present invention, the proportion of the mass of the ammonium cation species in formula (1) to the total mass of the organic cation species is preferably 50% by mass or more and 100% by mass or less. Having the mass of the ammonium cation species within this range enhances the storage stability of the resin composition of the present invention during frozen storage. The total mass of the organic cation species and the mass of the ammonium cation species can be determined by cation chromatography.

[0037] In the resin composition of the present invention, it is preferable that the compound represented by formula (1) contains a compound having a maximum absorption wavelength in the range of 500 nm to less than 580 nm in the region of 350 nm to 700 nm, and a compound having a maximum absorption wavelength in the range of 580 nm to 700 nm in the region of 350 nm to 700 nm. By including these compounds, the transmittance of the cured product can be reduced over a wide range of the visible light region. Furthermore, if necessary, the cured product can be made black by using in combination with the (C) thermochromic compound described later.

[0038] Examples of compounds represented by formula (1) that have a maximum absorption wavelength in the range of 500 nm to less than 580 nm in the region of 350 nm to 700 nm include compounds having the anionic moieties of CI Acid Red 52 and 289. Examples of compounds represented by formula (1) that have a maximum absorption wavelength in the range of 580 nm to 700 nm in the region of 350 nm to 700 nm include compounds having the anionic moieties of CI Acid Blue 83 and 90.

[0039] In the resin composition of the present invention, the total mass of total chlorine atoms and total bromine atoms contained in the resin composition is preferably 150 ppm by mass or less, more preferably 100 ppm by mass or less, and even more preferably less than 2 ppm by mass, which is the detection limit of combustion ion chromatography, relative to the total mass of solids in the resin composition. By setting the total amount of total chlorine atoms and total bromine atoms contained in the resin composition to 150 ppm by mass or less relative to the solids of the resin composition, it is possible to suppress the deterioration of electrodes and light-emitting layers of organic EL display devices having a cured product of the resin composition, and improve long-term reliability. The total mass of total chlorine atoms and total bromine atoms contained in the resin composition can be measured, for example, by combustion ion chromatography, in which the resin composition is burned in the combustion tube of an analytical instrument, the generated gas is absorbed into a solution, and a portion of the absorbent solution is analyzed by ion chromatography.

[0040] <(A) Alkali-soluble resin> The resin composition of the present invention contains (A) an alkali-soluble resin. An alkali-soluble resin is a resin having a dissolution rate of 50 nm / min or more, as defined below. Specifically, it is a resin having a dissolution rate of 50 nm / min or more, determined from the decrease in film thickness when a solution of resin dissolved in γ-butyrolactone is applied to a silicon wafer, pre-baked at 120°C for 4 minutes to form a pre-baked film with a thickness of 10 μm ± 0.5 μm, the pre-baked film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ± 1°C for 1 minute, and then rinsed with pure water.

[0041] (A) Alkali-soluble resins preferably have acidic groups in the structural units of the resin and / or at the ends of their main chains in order to impart alkali solubility. Preferred acidic groups include carboxyl groups, hydroxyl groups, sulfonic acid groups, and thiol groups.

[0042] (A)Specific examples of alkali-soluble resins include polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, phenolic resins, polymers made from radical polymerizable monomers having alkali-soluble groups, siloxane polymers, cyclic olefin polymers, and cardo resins. (A)The alkali-soluble resin may contain two or more of these resins. (A)It is preferable that the alkali-soluble resin contains one with high heat resistance. In addition, in order to obtain excellent properties as a planarization film, pixel division layer, partition, and protective film used in organic light-emitting devices, display devices, and semiconductor elements, it is preferable that the alkali-soluble resin (A) contains one with a low amount of outgassing at high temperatures of 200°C or higher after heat treatment. Specifically, it is preferable that the alkali-soluble resin (A) contains one or more selected from the group consisting of polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, and copolymers thereof.

[0043] This document describes polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof. Polyimides are not particularly limited as long as they have an imide ring, and polybenzoxazoles are not particularly limited as long as they have a benzoxazole ring. Similarly, polyimide precursors are not particularly limited as long as they have a structure that becomes a polyimide with an imide ring upon dehydration and cyclization, and polybenzoxazole precursors are not particularly limited as long as they have a structure that becomes a polybenzoxazole with a benzoxazole ring upon dehydration and cyclization.

[0044] (A) More preferably used as alkali-soluble resins include polyimides, polyimide precursors, polybenzoxazoles, and polybenzoxazole precursors.

[0045] Polyimide has a structural unit represented by formula (5).

[0046] [ka]

[0047] In formula (5), R 56 R is a 4-10 valent organic group. 57 R represents a 2- to 10-valent organic group. 58 and R 59 Each of these independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, or a substituent represented by formula (6) or formula (7). p represents an integer from 0 to 6, and q represents an integer from 0 to 8, where p + q > 0.

[0048] [ka]

[0049] In equations (6) and (7), R 60 ~R 62 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. The alkyl group, acyl group, and aryl group may be either unsubstituted or substituted.

[0050] The polyimide precursor has a structural unit represented by formula (8).

[0051] [ka]

[0052] In formula (8), R 63 R is a 4-10 valent organic group. 64 R represents a 2- to 10-valent organic group. 65 R represents a substituent represented by formula (6) or formula (7), 66 R represents a hydroxyl group, a sulfonic acid group, or a thiol group. 67 r represents a hydroxyl group, a sulfonic acid group, a thiol group, or a substituent represented by formula (6) or formula (7). r represents an integer from 2 to 8, s represents an integer from 0 to 6, and t represents an integer from 0 to 8, with 2 ≤ r + s ≤ 8.

[0053] Polybenzoxazoles have a structural unit represented by formula (9).

[0054] [ka]

[0055] In formula (9), R 68 R is a 2-10 valent organic group. 69 R represents a 4- to 10-valent organic group with an aromatic structure. 70 and R 71 Each of these independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, or a substituent represented by formula (6) or formula (7). u represents an integer from 0 to 8, and v represents an integer from 0 to 6, where u + v > 0.

[0056] The polybenzoxazole precursor has a structural unit represented by formula (10).

[0057] [ka]

[0058] In formula (10), R 72 R is a 2-10 valent organic group having an aromatic structure. 73 R represents an organic group with 4 to 10 valencies. 74 R represents a sulfonic acid group, a thiol group, or a substituent represented by formula (6) or formula (7), 75 x represents a hydroxyl group, carboxyl group, sulfonic acid group, thiol group, or substituent represented by formula (6) or formula (7). w represents an integer from 2 to 8, x represents an integer from 0 to 8, and y represents an integer from 0 to 6, with 2 ≤ w + y ≤ 8.

[0059] It is preferable that one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof have 5 to 100,000 structural units represented by formula (5), formula (8), formula (9), or formula (10). In addition, one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof may have other structural units in addition to the structural units represented by formula (5), formula (8), formula (9), or formula (10). In this case, it is preferable that one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof have 50 mol% or more of the structural units represented by formula (5), formula (8), formula (9), or formula (10) of the total number of structural units, and more preferably 70 mol% or more.

[0060] R in equation (5) 56 -(R 58 ) p , and (R in equation (8) 65 ) r -R 63 -(R 66 ) s The symbol represents a residue of a tetracarboxylic acid or a derivative thereof. Examples of residues of tetracarboxylic acid derivatives include residues of tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride, or tetracarboxylic acid active diester.

[0061] Examples of residues of tetracarboxylic acids or their derivatives include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3, Examples include 4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aromatic tetracarboxylic acids with the structures shown below, as well as aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid, or residues such as their tetracarboxylic dianhydrides, tetracarboxylic dichlorides, or tetracarboxylic active diesters.

[0062] [ka]

[0063] In the formula, R 76 R represents an oxygen atom, C(CF3)2, or C(CH3)2. 77 and R 78 Each of these independently represents either a hydrogen atom or a hydroxyl group.

[0064] R in equation (9) above 68 -(R 70 ) u , and R in equation (10) 72 -(R 74 ) xThe ∫ represents a residue of a dicarboxylic acid or its derivative. Examples of residues of dicarboxylic acid derivatives include residues of dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.

[0065] Examples of residues of dicarboxylic acids or their derivatives include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc., or residues of their dicarboxylic acid anhydrides, dicarboxylic acid chlorides, and dicarboxylic acid active esters. Examples of residues of tricarboxylic acids or their derivatives include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., or residues of their tricarboxylic acid anhydrides, tricarboxylic acid chlorides, and tricarboxylic acid active esters.

[0066] R in equation (5) 57 -(R 59 ) q and R in equation (8) 64 -(R 67 ) t represents a residue of a diamine or a derivative thereof. Also, R in equation (9) 69 -(R 71 ) v and (OH) in formula (10) w -R 73 -(R 75 ) y This represents a bisaminophenol compound or its derivative residue, among other diamines. Examples of diamines and bisaminophenol derivatives include diisocyanate compounds or trimethylsilylated diamines.

[0067] Examples of residues of diamine and bisaminophenol compounds or their derivatives include: 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4 Examples include '-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-3,3'-dihydroxybenzidine, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, or compounds in which at least some of the hydrogen atoms of the aromatic rings of these are substituted with alkyl groups, hydroxyl groups, or halogen atoms, as well as aliphatic cyclohexyldiamines, methylenebiscyclohexylamines, and residues of diamines having the structures shown below. Two or more of these may be used.

[0068] [ka]

[0069] In the formula, R 76 R represents an oxygen atom, C(CF3)2, or C(CH3)2. 77 ~R 80 Each of these independently represents either a hydrogen atom or a hydroxyl group.

[0070] Furthermore, by encapsulating the ends of these alkali-soluble resins with monoamines, acid anhydrides, acid chlorides, or monocarboxylic acids that have acidic groups, alkali-soluble resins with acidic groups at the ends of the main chain can be obtained.

[0071] Preferred examples of monoamines having such acidic groups include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used.

[0072] Furthermore, preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic anhydride; monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, and 4-carboxythiophenol; monoacid chloride compounds in which the carboxyl groups of these are acid-chloridized; and active ester compounds obtained by the reaction of monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. Two or more of these may be used.

[0073] (A) Alkali-soluble resins used in resin compositions are synthesized by known methods. In the case of polyimide precursors, such as polyamic acids and polyamic acid esters, they can be synthesized by methods such as reacting tetracarboxylic dianhydride with a diamine compound at low temperature, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol and then acid-chloridizing the remaining dicarboxylic acid and reacting it with an amine.

[0074] In the case of polyimides, for example, they can be obtained by dehydrating and cyclizing a polyamic acid or polyamic acid ester obtained by the method described above through heating or chemical treatment with an acid or base.

[0075] Polybenzoxazole precursors, such as polyhydroxyamides, can be produced by condensing a bisaminophenol compound with a dicarboxylic acid. Specifically, this can be done by reacting a dehydrating condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding the bisaminophenol compound, or by adding a solution of dicarboxylic acid dichloride dropwise to a solution of a bisaminophenol compound with a tertiary amine such as pyridine.

[0076] In the case of polybenzoxazoles, for example, they can be obtained by dehydrating and cyclizing polyhydroxyamides obtained by the aforementioned method through heating or chemical treatment with acids or bases.

[0077] (A) From the viewpoint of obtaining excellent properties as a planarization film, pixel splitting layer, partition, and protective film used in organic light-emitting devices, display devices, and semiconductor elements, the content of the alkali-soluble resin is preferably 0.5% by mass or more and 50% by mass or less per 100% by mass of the resin composition, and more preferably 1% by mass or more and 30% by mass or less.

[0078] <(B) Photosensitive compound> The resin composition of the present invention preferably further contains (B) a photosensitive compound. By containing (B) a photosensitive compound, the resin composition becomes a photosensitive resin composition, enabling pattern processing by photolithography. Examples of (B) a photosensitive compound include photoacid generators and photopolymerization initiators. From the viewpoint of resolution, it is preferable to include a photoacid generator as the photosensitive compound.

[0079] The photoacid generator may contain quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, etc. (B) The photosensitive compound preferably contains a quinone diazide compound. Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a polyhydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide-bonded to a polyamino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxypolyamino compound. Among these, those in which the sulfonic acid of quinone diazide is ester-bonded to a polyhydroxy compound are preferred. In particular, in the resin composition of the present invention, the quinone diazide compound contains a compound in which the sulfonic acid of quinone diazide is ester-bonded to a hydroxyl group of a polyhydroxy compound, and it is more preferable that the proportion of hydroxyl groups ester-bonded to the sulfonic acid of quinone diazide is 50 mol% or more and 90 mol% or less relative to 100 mol% of the total hydroxyl groups. By including a quinone diazide compound that is substituted by 50 mol% or more, the affinity of the quinone diazide compound for alkaline aqueous solutions is reduced, significantly decreasing the solubility of the unexposed resin composition in alkaline aqueous solutions. Furthermore, exposure causes the quinone diazide sulfonyl group to change to indene carboxylic acid, resulting in a high dissolution rate of the exposed resin composition in alkaline aqueous solutions. As a result, the dissolution rate ratio between the exposed and unexposed parts of the composition is increased, allowing for the acquisition of patterns with high resolution. Additionally, including a quinone diazide compound that is substituted by 90 mol% or less can suppress residue at the pattern openings. By using such a quinone diazide compound, a positive-type photosensitive resin composition that is sensitive to the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a typical mercury lamp can be obtained. Moreover, the photoacid generator may be used alone or in combination of two or more types, allowing for the acquisition of highly sensitive photosensitive resin compositions.

[0080] The quinone diazide can preferably be either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of mercury lamps and is suitable for g-line and full-wavelength exposure. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of mercury lamps and is suitable for i-line exposure. In the present invention, it is preferable to select either the 4-naphthoquinone diazidosulfonyl ester compound or the 5-naphthoquinone diazidosulfonyl ester compound depending on the exposure wavelength. Furthermore, it is possible to obtain a naphthoquinone diazidosulfonyl ester compound by using both a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group in the same molecule, or to use both a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound.

[0081] The molecular weight of the photoacid generator is preferably 300 or more, more preferably 350 or more, preferably 3000 or less, and more preferably 1500 or less, from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the cured product obtained by heat treatment.

[0082] (B) The content of the photosensitive compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less, per 100 parts by mass of (A) alkali-soluble resin. If the content is between 1 and 100 parts by mass, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance, and mechanical properties of the cured product after heat treatment.

[0083] <(C) Thermochromic compound> The resin composition of the present invention preferably further contains a (C) thermochromic compound. The (C) thermochromic compound is a compound that, before heating, does not have a maximum absorption wavelength in the region between 350 nm and 700 nm, but upon heating at 120°C or higher, produces a maximum absorption wavelength in any of the regions between 350 nm and 700 nm (hereinafter sometimes referred to as "thermochromic"). The (C) thermochromic compound preferably contains a compound that, upon heating at 120°C or higher, produces a maximum absorption wavelength in any of the regions between 350 nm and 500 nm within the region between 350 nm and 700 nm. By using such a (C) thermochromic compound, the transmittance in the 350 nm to 500 nm range can be significantly reduced after heating at 120°C or higher, and a cured product with higher blackness can be obtained.

[0084] (C) For the thermochromic compound, a thermochromic compound that develops color at temperatures above 180°C is preferred. The higher the temperature at which the thermochromic compound develops color, the better its heat resistance under high-temperature conditions, and the less it fades when exposed to ultraviolet and visible light for extended periods, resulting in superior lightfastness.

[0085] (C) The thermochromic compound may be a general heat-sensitive dye or pressure-sensitive dye, or it may be any other compound. Examples of these thermochromic compounds include those that change color by altering their chemical structure or charge state due to the action of acidic groups present in the system during heat treatment at 120°C or higher, or those that undergo thermal oxidation reactions at 120°C or higher due to the presence of oxygen in the air, resulting in thermal coloration. Examples of the skeletal structure of the thermochromic compound include the triarylmethane skeleton, diarylmethane skeleton, fluorane skeleton, bislactone skeleton, phthalide skeleton, xanthene skeleton, rhodamine lactam skeleton, fluorene skeleton, phenothiazine skeleton, phenoxazine skeleton, and spiropyran skeleton. Specifically, examples include the compounds described in Japanese Patent Publication No. 2004-326094. Among these, hydroxyl group-containing compounds having a triarylmethane skeleton are particularly preferred because they have a high temperature at which they develop color and excellent heat resistance. These may be contained individually or in combination.

[0086] Furthermore, (C) the thermochromic compound contains an aromatic hydrocarbon compound having at least one aromatic CH bond and at least three phenolic hydroxyl groups within one aromatic ring, and it is also preferable that it contains a triazine ring-containing compound represented by formula (4).

[0087] [ka]

[0088] In formula (4), R 50 ~R 55 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, and an alkoxymethyl group having 2 to 10 carbon atoms. However, R 50 ~R 55 Of these, at least one is a methylol group or an alkoxymethyl group having 2 to 10 carbon atoms. The resin composition of the present invention contains these compounds, which allows it to develop color upon heating regardless of the atmosphere during curing, and to reduce the transmittance in the 300nm to 500nm range after curing.

[0089] Examples of aromatic hydrocarbons having at least one aromatic CH bond and three phenolic hydroxyl groups within one aromatic ring include phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, galacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, and 2,3,4,4'-tetrahydroxybenzophenone. Examples of aromatic hydrocarbons having at least one aromatic CH bond and four or more phenolic hydroxyl groups within one aromatic ring include 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizalin. In particular, from the viewpoint of further reducing the transmittance in the 300nm to 500nm range after curing, it is preferable that at least one substitution position of any other phenolic hydroxyl group relative to any one phenolic hydroxyl group is either ortho or para, and more preferably para. Examples of compounds in which at least one substitution position of any other phenolic hydroxyl group relative to any one phenolic hydroxyl group is para include 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizalin.

[0090] Furthermore, the triazine ring-containing compound represented by formula (4) has R in formula (4). 50 ~R 55Of these, at least one is a methylol group or an alkoxymethyl group, preferably two or more, more preferably three or more, even more preferably four or more, and most preferably all six are methylol groups or alkoxymethyl groups. Examples of alkoxymethyl groups include methoxymethyl group, ethoxymethyl group, propoxymethyl group, and butoxymethyl group.

[0091] The content of the (C) thermochromic compound used in the present invention is preferably 5 to 80 parts by mass, and particularly preferably 10 to 60 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. If the content of the (C) thermochromic compound is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet-visible light region can be reduced. If it is 80 parts by mass or less, the heat resistance and strength of the cured product can be maintained and the water absorption rate can be reduced.

[0092] <Other colorants> The resin composition of the present invention may also contain other colorants. Such colorants include dyes, organic pigments, and inorganic pigments, and can be used depending on the purpose.

[0093] The resin composition of the present invention may contain various known additives other than the compound represented by formula (1), (A) alkali-soluble resin, (B) photosensitive compound, and (C) thermochromic compound, as well as other colorants, such as thermal crosslinking agents, compounds having phenolic hydroxyl groups, adhesion improvers, and surfactants.

[0094] <Solvent> The resin composition of the present invention may contain a solvent. Examples of solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyrate amide, and methoxy-N,N-dimethylpropionamide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be included. The solvent content is preferably 100 parts by mass or more per 100 parts by mass of alkali-soluble resin (A) in order to dissolve the composition. Furthermore, from the viewpoint of coatability, the solvent content is preferably 10,000 parts by mass or less, and more preferably 5,000 parts by mass or less per 100 parts by mass of alkali-soluble resin (A).

[0095] The resin composition of the present invention can be used to form insulating films, protective films, and planarization films of semiconductor elements and display devices. In particular, it is preferably used to form planarization layers and pixel division layers of organic EL display devices because it exhibits excellent high heat resistance and low outgassing properties for planarization layers and pixel division layers, and is especially preferably used to form pixel division layers of organic EL display devices because it can improve the contrast of organic EL display devices.

[0096] <Method for producing resin compositions> Next, an example of a method for producing the resin composition of the present invention will be described.

[0097] A resin composition can be obtained by mixing the following components of the present invention: a compound represented by formula (1), (A) an alkali-soluble resin, optionally (B) a photosensitive compound, (C) a thermochromic compound, other colorants, thermal crosslinking agents, compounds having phenolic hydroxyl groups, adhesion improvers, surfactants, solvents, etc. The resin composition used in the method for producing the resin composition film of the present invention, described later, preferably contains a solvent to dissolve each of the above components. In such cases, heating and stirring are methods to promote dissolution. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually room temperature to 80°C. In this specification, room temperature is defined as 25°C. Furthermore, the order in which each component is dissolved is not particularly limited; for example, a method of sequentially dissolving compounds starting with those with low solubility in the solvent is possible. When stirring, the rotation speed is preferably set within a range that does not impair the performance of the resin composition, and is usually 200 rpm to 2000 rpm. Even when stirring, heating may be performed as needed, and is usually room temperature to 80°C. Furthermore, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of other components due to bubble formation.

[0098] The obtained resin composition is preferably filtered using a filtration filter to remove dirt and particles. The pore size of the filter can be, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, or 0.02 μm, but is not limited to these. The material of the filtration filter can be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), but polyethylene or nylon is preferred. Furthermore, if the resin composition contains organic pigments, it is preferable to use a filtration filter with a pore size larger than the particle size of these pigments.

[0099] <Cured product> A first embodiment of the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. A second embodiment of the cured product of the present invention is a cured product containing the compound of the present invention.

[0100] The cured product of the present invention can be obtained, for example, by applying a resin composition containing the compound represented by formula (1) described above to a substrate or the like, and curing it by heat treatment. The heat treatment conditions are preferably 200°C or higher, more preferably 250°C or higher. Furthermore, the heat treatment conditions are preferably 400°C or lower, and more preferably 350°C or lower.

[0101] <Method for manufacturing a cured product> An example of a method for producing the cured product of the present invention will be described.

[0102] One example of a method for producing a cured product includes, in this order: (1) applying the above-mentioned resin composition to a substrate to form a coating film; (2) exposing the coating film to an activated light to obtain an exposed coating film; (3) developing the exposed coating film using an alkaline solution to obtain a developed coating film; and (4) heating the developed coating film to obtain a cured product.

[0103] (1) In the step of forming a coating film of the resin composition, the resin composition of the present invention is applied by, for example, a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc., to obtain a coating film of the resin composition. Prior to application, the substrate to which the resin composition will be applied may be pre-treated with the adhesion improving agent described above. For example, a method of treating the substrate surface is to use a solution obtained by dissolving the adhesion improving agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate at a concentration of 0.5 to 20% by mass. Examples of substrate surface treatment methods include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment. In the step of drying the coating film, the formed coating film is subjected to vacuum drying as needed, and then the coating film is obtained by heat treatment using a hot plate, oven, infrared rays, etc., at a temperature of 50°C to 180°C for 1 minute to several hours.

[0104] Next, (2) the process of exposing the above coating film to light will be explained. The above coating film is irradiated with an activated light (hereinafter sometimes referred to as exposure). At this time, exposure may be performed via a photomask having a desired pattern as needed, or the coating film may be directly exposed with a laser or the like. Activated light sources used for exposure include ultraviolet light, visible light, electron beams, and X-rays, but in this invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

[0105] Next, we will explain the process of (3) developing the exposed coating film using an alkaline solution to obtain the developed coating film. The exposed coating film is developed using an alkaline solution to remove the exposed areas of the coating film. The developer at this time is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. In some cases, one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, or dimethylacrylamide, alcohols such as methanol, ethanol, or isopropanol, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, or ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutyl ketone may be added to these alkaline aqueous solutions. Possible development methods include spray, paddle, immersion, and ultrasonic.

[0106] Next, it is preferable to rinse the pattern formed by development with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0107] Next, (4) the process of obtaining a cured product by heat-treating the developed coating film will be explained. By heat-treating the developed coating film, residual solvents and components with low heat resistance can be removed, thereby improving the heat resistance and chemical resistance of the cured product. This heat treatment is performed by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. For example, a method of heat treatment at 230°C for 60 minutes can be used. In this invention, the heat treatment conditions are preferably 200°C or higher, and more preferably 230°C or higher. Furthermore, the heat treatment conditions are preferably 400°C or lower, and more preferably 350°C or lower.

[0108] <Display device> The display device of the present invention comprises the cured product of the present invention. The cured resin composition is included in the planarization layer and pixel division layer of a display device having, in this order, a substrate on which a TFT is formed, a planarization layer on a drive circuit, a pixel division layer on a first electrode, a display element, and a second electrode. Examples of display devices with such a configuration include liquid crystal displays and organic EL displays. In particular, it is especially suitable for use in organic EL displays where high heat resistance and low outgassing are required for the planarization layer and pixel division layer, and is especially suitable for use in the pixel division layer because it can improve the contrast of the organic EL display device.

[0109] The cured product obtained by curing the resin composition of the present invention may be used for either the planarization layer or the pixel division layer, or for both. An active matrix type display device has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass, and a planarization layer covering the irregularities thereon, and a display element is further provided on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer. [Examples]

[0110] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0111] <Evaluation of residual film percentage> The resin compositions prepared in the examples and comparative examples (hereinafter sometimes referred to as varnish) were applied by spin coating onto a glass substrate (manufactured by Geomatec Co., Ltd.; hereinafter referred to as "ITO substrate") on which ITO had been deposited by sputtering, using a spin coater (MS-A100; manufactured by Mikasa Corporation) to achieve a film thickness of 3.0 μm after heat treatment (curing). A pre-baked film was then prepared by pre-baking at 120°C for 120 seconds using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Corporation). The obtained pre-baked film was developed in a 2.38% by mass aqueous solution of tetramethylammonium (TMAH) for 60 seconds to obtain the desired film thickness, and then rinsed with pure water to obtain a developed film.

[0112] The film thickness of the pre-baked film and the developed film in the center of the substrate was measured using a stylus-type profiler (P-15; manufactured by KLA-Tencor). The residual film percentage was calculated from these values ​​using the following formula, and the results were determined as follows. Residual film percentage [%] = (Thickness of developing film) / (Thickness of pre-baked film) × 100 A: Residual film rate is between 80% and 100% B: Residual film rate is 50% or more but less than 80% C: Residual film rate is less than 50%.

[0113] (2) Evaluation of changes in opening dimensions The pre-baked films obtained using the above procedure were subjected to 0-1000 mJ / cm² of radiation using a GHI-line mask aligner (PEM-6M; manufactured by Union Optics Co., Ltd.). 2Exposure was performed using a grayscale mask (MDRM MODEL 4000-5-FS; Opto-Line International) for sensitivity measurement at the specified exposure dose. After exposure, the material was developed for 60 seconds with a 2.38% by mass aqueous solution of tetramethylammonium (TMAH) to obtain the desired film thickness, and then rinsed with pure water to obtain a relief pattern. The pattern was observed at 100x magnification using an FDP microscope MX61 (Olympus Corporation), and the aperture size (aperture size after development) at the exposure dose that formed a 20 μm line-and-space pattern with a 1:1 width was measured. Subsequently, the obtained pattern was cured in an oven at 230°C under a nitrogen atmosphere for 60 minutes, and the aperture size (aperture size after curing) at the same exposure dose as above was measured. From these measurements, the change in aperture size was calculated using the following formula, and the following determination was made. Aperture change [μm] = (Aperture after development) - (Aperture after curing) A: The change in aperture size is between 0.0 μm and 0.1 μm. B: Aperture dimension change is greater than 0.1 μm and less than or equal to 0.2 μm. C: The change in aperture size is greater than 0.2 μm or less than 0.0 μm.

[0114] (3) Evaluation of reliability Reliability was evaluated by the luminous area ratio of an organic EL display device having a cured product made from the resin compositions prepared in the examples and comparative examples as a pixel splitting layer.

[0115] Figures 1(a) to 1(d) show schematic diagrams of the substrates used. First, a 10 nm transparent ITO conductive film was formed on the entire surface of a 38 × 46 mm alkali-free glass substrate 1 by sputtering and etched as the first electrode 2. At the same time, an auxiliary electrode 3 was also formed to extract the second electrode (Figure 1(a)). The obtained substrate was ultrasonically cleaned for 10 minutes with "Semicoclean" (registered trademark) 56 (product name, manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water. Next, the photosensitive resin composition prepared in each example and comparative example was applied to the entire surface of this substrate by spin coating and pre-baked on a hot plate at 100°C for 2 minutes. After UV exposure of this film through a photomask, it was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution to dissolve only the exposed areas, and then rinsed with pure water. The obtained pattern was cured in an oven at 230°C under a nitrogen atmosphere for 60 minutes. In this way, a pixel division layer 4 was formed, limited to the effective area of ​​the substrate, with openings measuring 70 μm in width and 260 μm in length arranged at a pitch of 155 μm in the width direction and 465 μm in the length direction, and each opening exposing the first electrode (Figure 1(b)). These openings will ultimately become light-emitting pixels. The effective area of ​​the substrate was 16 mm square, and the thickness of the insulating layer was approximately 1.0 μm.

[0116] Next, an organic EL display device was fabricated using a substrate on which the first electrode 2, auxiliary electrode 3, and pixel division layer 4 were formed. After nitrogen plasma treatment as a pretreatment, an organic EL layer 5 including the light-emitting layer was formed by vacuum deposition (Figure 1(c)). The vacuum level during deposition was 1 × 10⁻⁶. -3 The temperature was below Pa, and the substrate was rotated relative to the deposition source during deposition. First, compound (HT-1) was deposited as a hole injection layer at 10 nm, and compound (HT-2) was deposited as a hole transport layer at 50 nm. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm with a doping concentration of 10%. Then, compound (ET-1) and (LiQ) were layered as electron transport materials in a volume ratio of 1:1 to a thickness of 40 nm. The structures of the compounds used in the organic EL layer are shown below.

[0117] [ka]

[0118] Next, after depositing a 2nm layer of compound (LiQ), MgAg was co-deposited at a volume ratio of Mg to Ag of 10:1 to form the second electrode 6 (Figure 1(d)). Finally, the device was sealed by bonding a cap-shaped glass plate using an epoxy resin adhesive under a low-humidity nitrogen atmosphere, and four 5mm square light-emitting devices were fabricated on a single substrate. The film thickness referred to here is the value displayed on a quartz crystal oscillator film thickness monitor.

[0119] The fabricated organic EL display device was set to 10 mA / cm². 2 The device was driven by DC to emit light, and the light-emitting area of ​​the light-emitting pixel (light-emitting area before UV light irradiation) was measured. Next, the device was placed with the light-emitting surface facing upwards on a hot plate heated to 80°C, with a wavelength of 365 nm and an illuminance of 0.6 mW / cm². 2 UV light was irradiated. After 1000 hours, the reading was 10 mA / cm². 2 The light was emitted using DC drive, and the luminescence area of ​​the light-emitting pixel (luminescence area after UV light irradiation) was measured. From these measurements, the luminescence area ratio was calculated using the following formula, and the reliability was determined from this value as follows. Emission area percentage [%] = (Emission area after UV light irradiation) / (Emission area before UV light irradiation) × 100 A: Luminous area ratio is between 75% and 100%. B: Luminous area ratio is between 50% and 75%. C: Emitting area ratio is 50% or less.

[0120] (4) Evaluation of the frozen storage stability of the resin composition Using a coating and developing system "CLEAN TRACK ACT-12" manufactured by Tokyo Electron Ltd., each varnish, which had been filtered and stored in a -18°C freezer for 60 days, was applied to a 12-inch Si wafer. The wafers were then dried on a hot plate at 100°C for 3 minutes to obtain a photosensitive resin film with a thickness of 1000 nm. The number of foreign particles larger than 0.27 μm was measured on the obtained photosensitive resin film using a wafer surface inspection system "WM-10" manufactured by Topcon Corporation. The measurement area was approximately 201 cm² inside a circle with a radius of 8 cm from the center of the wafer. 2The coating film is 1 cm thick. 2 The number of foreign objects per unit area (defect density) was calculated. The defect density per substrate was 1.00 defects / cm³. 2 If it is less than 1.00, it is marked "A", 1.00 pieces / cm 2 More than 3.00 pieces / cm 2 If it is less than 3.00 pieces / cm, it is marked "B". 2 If the above conditions were met, the result was judged as "C".

[0121] [Synthesis Example 1] 20.3 g (0.035 mol) of CI Acid Red 52 as the anionic component and 400 g of pure water were added to a separable flask and stirred at room temperature for 30 minutes. Then, an aqueous solution of 16.9 g (0.039 mol) of tetrahexylammonium bromide dissolved in 1700 g of pure water was added as the cationic component, and the mixture was stirred at room temperature for 60 minutes. The reaction mixture was then filtered to obtain a red solid. This solid was dried under reduced pressure at 60°C for 8 hours to obtain compound z-1 represented by formula (1). The obtained compound was analyzed by hydrogen nuclear magnetic resonance spectroscopy ( 1 Identification was performed using 1H NMR (JNM-ECZ400R; manufactured by JEOL Ltd.).

[0122] 1 H NMR(400MHz,DMSO-d6)δ:8.26(d,J=2.0Hz,1H,ArH),7.72(dd,J1=8.0Hz,J2=2.0Hz, 1H,ArH),7.14(d,J=8.0Hz,1H,ArH),7.03(s,4H,ArH),6.92(s,2H,ArH),3.66-3.61( m,8H,ArNCH2),3.18-3.13(m,8H,NCH2),1.56(br,8H,NCH2CH2),1.29(br,24H,N(CH2 )2(CH2)3),1.21(t,J=6.8Hz,12H,ArNCH2CH3),0.88(t,J=7.0Hz,12H,N(CH2)5CH3).

[0123] [Synthesis Example 2] Compound z-2, represented by formula (1), was obtained in the same manner as in Synthesis Example 1, except that tetrapentylammonium bromide 14.8 g (0.039 mol) was used as the cationic component instead of tetrahexylammonium bromide 16.9 g (0.039 mol). The identification results are shown below.

[0124] 1 H NMR(400MHz,DMSO-d6):8.26(d,J=2.0Hz,1H,ArH),7.72(dd,J1=8.0Hz,J2=2.0Hz,1H,ArH),7.14(d,J=8.0Hz,1H,ArH),7.03(s,4H,ArH),6.92(s,2 H,ArH),3.66-3.61(m,8H,ArNCH2),3.18-3.14(m,8H,NCH2),1.61-1.54(m,8H,NCH2CH2),1.38-1.15(m,28H),0.89(t,J=7.0Hz,12H,N(CH2)4CH3).

[0125] [Synthesis Example 3] Compound z-3, represented by formula (1), was obtained in the same manner as in Synthesis Example 1, except that CI Acid Red 289 23.7 g (0.035 mol) was used as the anionic component instead of CI Acid Red 52 20.3 g (0.035 mol). The identification results are shown below.

[0126] 1 H NMR(400MHz,DMSO-d6):9.92(s,2H,ArNH),8.04-7.18(m,14H,ArH),6.01(s,2H,ArH),3.18-3.13(m,8H,NCH2),2.2 0-2.15(m,6H,ArCH3),1.56(br,8H,NCH2CH2),1.29(br,24H,N(CH2)2(CH2)3),0.88(t,J=7.0Hz,12H,N(CH2)5CH3).

[0127] [Synthesis Example 4] Compound z-4, represented by formula (1), was obtained in the same manner as in Synthesis Example 1, except that CI Acid Blue 90 29.9 g (0.035 mol) was used as the anionic component instead of CI Acid Red 52 20.3 g (0.035 mol). The identification results are shown below.

[0128] 1 H NMR(400MHz,DMSO-d6):10.03(s,1H,ArNH),7.59-7.50(m,4H,ArH),7.39-7.17(m,8H,ArH),7.04-6.78(m,1 0H,ArH),4.80(s,4H,ArCH2N),4.04(m,2H,ArOCH2),3.68-3.62(m,4H,ArNCH2),3.15(m,8H,NCH2),1.79(br s,6H,ArCH3),1.56(br,8H,NCH2CH2),1.35-1.19(m,33H),0.88(t,J=7.0Hz,12H,N(CH2)5CH3).

[0129] [Synthesis Example 5] Compound z-5, represented by formula (1), was obtained in the same manner as in Synthesis Example 1, except that 29.9 g (0.035 mol) of CI Acid Blue 90 was used as the anionic component instead of 20.3 g (0.035 mol) of CI Acid Red 52, and 14.8 g (0.039 mol) of tetrapentylammonium bromide was used as the cationic component instead of 16.9 g (0.039 mol) of tetrahexylammonium bromide. The identification results are shown below.

[0130] 1 1H NMR (400MHz, DMSO-d6): 1H NMR(400MHz,DMSO-d6):10.03(s,1H,ArNH),7.59-7.50(m,4H,ArH),7.39-7.17(m,8H,ArH),7.04-6.78(m,10H ,ArH),4.80(s,4H,ArCH2N),4.04(m,2H,ArOCH2),3.68-3.62(m,4H,ArNCH2),3.18-3.14(m,8H,NCH2),1.79(br s,6H,ArCH3),1.61-1.54(m,8H,NCH2CH2),1.39-1.19(m,33H),0.89(t,J=7.0Hz,12H,N(CH2)4CH3).

[0131] [Synthesis Example 6] Compound z-6, represented by formula (1), was obtained in the same manner as in Synthesis Example 1, except that CI Acid Blue 83 28.9 g (0.035 mol) was used as the anionic component instead of CI Acid Red 52 20.3 g (0.035 mol). The identification results are shown below.

[0132] 1 H NMR(400MHz,DMSO-d6):9.68(s,1H,ArNH),7.60-7.50(m,4H,ArH),7.35-7.19(m,12H,ArH),7.07-6.97(m,8H,ArH),4.86(s,4H,ArCH2N),4.03(q,J= 6.9Hz,2H,ArOCH2),3.71-3.69(m,4H,ArNCH2),3.15(m,8H,NCH2),1.56(br,8H,NCH2CH2),1.35-1.22(m,25H),0.88(t,J=7.0Hz,12H,N(CH2)5CH3).

[0133] [Synthesis Example 7] Compound z-7, represented by formula (1), was obtained in the same manner as in Synthesis Example 1, except that 19.1 g (0.035 mol) of CI Acid Blue 1 was used as the anionic component instead of 20.3 g (0.035 mol) of CI Acid Red 52. The identification results are shown below.

[0134] 1H NMR(400MHz,DMSO-d6):8.19(d,J=1.6Hz,1H,ArH),7.62(dd,J1=8.0Hz,J2=1.6 Hz,1H,ArH),7.29(d,J=9.2Hz,4H,ArH),6.98-6.91(m,5H,ArH),3.62(q,J=6.9H z,ArNCH2),3.15(m,8H,NCH2),1.56(br,8H,NCH2CH2),1.29(br,24H,N(CH2)2(C H2)3),1.20(t,J=7.0Hz,12H,ArNCH2CH3),0.88(t,J=7.0Hz,12H,N(CH2)5CH3).

[0135] [Synthesis Example 8] Compound z-8 was obtained in the same manner as in Synthesis Example 1, except that tetradecylammonium bromide 21.5 g (0.039 mol) was used as the cationic component instead of tetrahexylammonium bromide 16.9 g (0.039 mol). The identification results are shown below.

[0136] 1 H NMR(400MHz,DMSO-d6):8.26(d,J=2.0Hz,1H,ArH),7.72(dd,J1=8.0Hz,J2=2.0Hz,1H,ArH),7.14(d,J=8.0Hz,1H,ArH),7.03(s,4H,ArH),6.92(s,2 H,ArH),3.66-3.61(m,8H,ArNCH2),3.18-3.14(m,8H,NCH2),1.61-1.54(m,8H,NCH2CH2),1.38-1.15(m,68H),0.86(t,J=7.0Hz,12H,N(CH2)9CH3).

[0137] [Synthesis Example 9] Compound z-9 was obtained in the same manner as in Synthesis Example 1, except that decyltripentylammonium bromide 14.7 g (0.039 mol) was used as the cationic component instead of decylammonium bromide 16.9 g (0.039 mol). The identification results are shown below.

[0138] 1H NMR(400MHz,DMSO-d6):8.26(d,J=2.0Hz,1H,ArH),7.72(dd,J1=8.0Hz,J2=2.0Hz,1H,ArH),7.14(d,J=8.0Hz,1H,ArH),7.03(s,4H) ,ArH),6.92(s,2H,ArH),3.66-3.61(m,8H,ArNCH2),3.18-3.14(m,8H),1.61-1.54(m,8H),1.38-1.15(m,38H),0.91-0.84(m,12H).

[0139] [Synthesis Example 10] Compound z-10 was obtained in the same manner as in Synthesis Example 1, except that tetrabutylammonium bromide 10.5 g (0.039 mol) was used as the cationic component instead of tetrahexylammonium bromide 16.9 g (0.039 mol). The identification results are shown below.

[0140] 1 H NMR(400MHz,DMSO-d6):8.26(d,J=2.0Hz,1H,ArH),7.72(dd,J1=8.0Hz,J2=2.0Hz,1H,ArH),7.14(d,J=8.0Hz,1H,ArH),7.03(s,4H,ArH),6.92(s,2 H,ArH),3.66-3.61(m,8H,ArNCH2),3.18-3.14(m,8H,NCH2),1.61-1.54(m,8H,NCH2CH2),1.38-1.15(m,20H),0.94(t,J=7.0Hz,12H,N(CH2)3CH3).

[0141] [Synthesis Example 11] Compound z-11 was obtained in the same manner as in Synthesis Example 1, except that 14.2 g (0.039 mol) of hexadecyltrimethylammonium bromide was used as the cationic component instead of 16.9 g (0.039 mol) of tetrahexylammonium bromide. The identification results are shown below.

[0142] 1H NMR(400MHz,DMSO-d6):8.26(d,J=2.0Hz,1H,ArH),7.72(dd,J1=8.0Hz,J2=2.0Hz,1H,ArH),7.14(d,J=8.0Hz,1H,ArH),7.03(s,4H,ArH),6.92(s,2H,Ar H),3.66-3.61(m,8H,ArNCH2),3.27-3.22(m,2H,NCH2),3.02(s,9H,NCH3),1 .70-1.62(m,2H,NCH2CH2),1.27-1.19(m,38H),0.85(t,J=7.0Hz,3H,N(CH2) 15 CH3).

[0143] Table 1 shows the anionic and cationic components used in synthesis examples 1 to 11.

[0144] [Table 1]

[0145] [Synthesis Example 12] In a three-necked flask, 18.31 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 17.4 g (0.3 mol) of propylene oxide, and 100 mL of acetone were weighed and dissolved. To this, a solution of 20.41 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 10 mL of acetone was added dropwise. After the addition was complete, the mixture was reacted at -15°C for 4 hours, and then allowed to return to room temperature. The precipitated white solid was filtered and vacuum-dried at 50°C. 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of 2-methoxyethanol, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced using a balloon, and the mixture was reacted at room temperature for 2 hours. After 2 hours, it was confirmed that the balloon did not deflate any further. After the reaction was complete, the catalyst, a palladium compound, was removed by filtration, and the compound was concentrated by distillation under reduced pressure to obtain a hydroxyl group-containing diamine compound (HA) with the structure shown below.

[0146] [ka]

[0147] Under a stream of dry nitrogen, 15.1 g (0.025 mol) of HA, 3.66 g (0.01 mol) of BAHF, and 0.62 g (0.0025 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter, SiDA) were dissolved in 200 g of N-methylpyrrolidone (NMP). 22.2 g (0.05 mol) of 2,2-(3,4-dicarboxyphenyl)hexafluoropropane (hereinafter, 6FDA) was added along with 50 g of NMP, and the mixture was stirred at 40°C for 1 hour. Then, 2.73 g (0.025 mol) of 3-aminophenol (hereinafter, MAP) was added, and the mixture was stirred at 40°C for 1 hour. Finally, a solution of 11.9 g (0.1 mol) of N,N-dimethylformamide dimethylacetal (hereinafter, DFA) diluted with 5 g of NMP was added, and the mixture was stirred at 40°C for 2 hours. After stirring was complete, the solution was added to 2 L of water, and the polymer solid precipitate was collected by filtration. The solution was then washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain (A) polyimide precursor resin a-1 as an alkali-soluble resin.

[0148] [Synthesis Example 13] Under a stream of dry nitrogen, 21.2 g (0.05 mol) of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) and 26.8 g (0.1 mol) of 5-naphthoquinone diazidosulfonic acid chloride were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. To this, 12.7 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After addition, the mixture was stirred at 40°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration and washed with 1 L of 1% hydrochloric acid water. After that, it was washed twice more with 2 L of water. The precipitate was dried in a vacuum dryer to obtain quinone diazide compound b-1 represented by the following formula.

[0149] The compounds shown in each example and comparative example are listed below.

[0150] [ka]

[0151] [Example 1] Under a yellow light, the following compounds were added: (A) compound z-1 obtained in Synthesis Example 1 as the compound represented by formula (1), (B) polyimide precursor resin a-1 obtained in Synthesis Example 12 as the alkali-soluble resin, (C) compound b-1 obtained in Synthesis Example 13 as the photosensitive compound, (C) compound c-1 as the thermochromic compound, (D-1) as the thermal crosslinking agent as an additive, and γ-butyrolactone (GBL) and ethyl lactate (EL) as solvents in the amounts shown in Table 1. The mixture was stirred and dissolved to prepare Composition 1.

[0152] For composition 1, the residual film ratio, aperture size change, and reliability were evaluated.

[0153] [Examples 2-11, Comparative Examples 1-3] Compositions 2 to 14 were prepared using the same method as in Example 1, with the compositions listed in Table 2. Compositions 2 to 14 were evaluated using the same method as in Example 1.

[0154] [Examples 12, 13] The frozen storage stability of compositions 1 and 11 was evaluated.

[0155] The composition and evaluation results of the resin compositions for each example and comparative example are shown in Tables 2 and 3.

[0156] [Table 2]

[0157] [Table 3]

[0158] Compositions 12-14 that did not contain the compound represented by formula (1) showed a low residual film rate. The resin composition containing the compound represented by formula (1) of the present invention was confirmed to have a high residual film rate.

Industrial Applicability

[0159] The compounds, resin compositions, and cured products of the present invention are suitably used for surface protective films of semiconductor elements, interlayer insulating films, pixel division layers of organic EEL elements, planarization films of TFT substrates for driving display devices using organic EL elements, wiring protective insulating films of circuit boards, on-chip microlenses of solid-state imaging devices, planarization films for various displays and solid-state imaging devices, and solder resists for circuit boards.

Explanation of Signs

[0160] 1: Glass substrate 2: First electrode 3: Auxiliary electrode 4: Pixel division layer 5: Organic EL layer 6: Second electrode

Claims

1. A compound represented by formula (1). 【Chemistry 1】 (In formula (1), A ｎ－ R is an n-valent anion represented by formula (2) or formula (3). １ ~R ４ Each of these is an alkyl group having 5 to 10 carbon atoms. n takes an integer from 1 to 3. 【Chemistry 2】 (In formula (2), R ５ to R ８ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ９ to R １４ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. R １５ to R １８ each independently represents a hydrogen atom, a halogen atom, -SO ３ H, -SO ３ － -SO ３ NR １９ R ２０ , -COOH, -COO － , -COOR ２１ , -CONR ２２ R ２３ , -OR ２４ , -NR ２５ R ２６ or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R １９ to R ２６ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ５ to R ８ and R １５ to R １８ at least one of which is a monovalent hydrocarbon group having 1 to 10 carbon atoms having -SO ３ － or -COO － , -SO ３ － or -COO － . X represents -SO ３ － or -COO － .) 【Transformation 3】 (In formula (3), R ２７ ~R ３０ Each of these independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. ３１ ~R ３６ Each of these independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. ３７ ~R ４１ These are, independently, a hydrogen atom, a halogen atom, and -SO4. ３ H, -SO ３ － , -SO ３ NR ４２ R ４３ , -COOH, -COO － , -COOR ４４ , -CONR ４５ R ４６ , -OR ４７ , -NR ４８ R ４９ Alternatively, it represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. ３７ ~R ４１ Among these, adjacent elements may be joined to each other, forming a ring structure. ４２ ~R ４９ Each of these independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. ２７ ~R ３０ and R ３７ ~R ４１ Of these, at least two are -SO ３ － Or -COO － A monovalent hydrocarbon group having 1 to 20 carbon atoms, -SO ３ － or -COO － (That is the case.)

2. In equation (1), R １ , R ２ , R ３ and R ４ The compound according to claim 1, wherein all substituents are identical.

3. R in equation (1) １ , R ２ , R ３ and R ４ The compound according to claim 1 or 2, wherein all of them are alkyl groups having 5 or 6 carbon atoms.

4. The compound according to claim 1 or 2, wherein the maximum absorption wavelength in the region of 350 nm to 700 nm is located in any of the regions of 500 nm to 700 nm.

5. A resin composition comprising the compound described in claim 1 and (A) an alkali-soluble resin.

6. The resin composition according to claim 5, wherein the proportion of the mass of the ammonium cation species in formula (1) to the total mass of organic cation species in the resin composition is 50% by mass or more and 100% by mass or less.

7. The compound according to claim 1 or 2, A compound having a maximum absorption wavelength in the range of 500 nm to less than 580 nm in the region of 350 nm to 700 nm, The resin composition according to claim 5 or 6, comprising a compound having a maximum absorption wavelength in the range of 580 nm to 700 nm in the region of 350 nm to 700 nm.

8. The resin composition according to claim 5 or 6, wherein the total mass of all chlorine atoms and all bromine atoms contained in the resin composition is 150 ppm by mass or less with respect to the total mass of solids in the resin composition.

9. Furthermore, the resin composition according to claim 5 or 6, further comprising (B) a photosensitive compound.

10. The resin composition according to claim 9, wherein the (B) photosensitive compound contains a quinone diazide compound.

11. The resin composition according to claim 10, wherein the quinone diazide compound contains a compound in which the sulfonic acid of quinone diazide is ester-bonded to the hydroxyl group of a polyhydroxy compound, and the proportion of hydroxyl groups ester-bonded to the sulfonic acid of quinone diazide is 50 mol% or more and 90 mol% or less of the total hydroxyl groups.

12. Furthermore, the resin composition according to claim 5 or 6, further comprising (C) a thermochromic compound.

13. The resin composition according to claim 12, wherein the (C) thermochromic compound contains a compound that, upon heating at 120°C or higher, produces a maximum absorption wavelength in any of the regions between 350 nm and 500 nm in the region between 350 nm and 700 nm.

14. The resin composition according to claim 12, wherein the (C) thermochromic compound contains an aromatic hydrocarbon compound having at least one aromatic C-H bond and at least three phenolic hydroxyl groups in one aromatic ring, and further contains a triazine ring-containing compound represented by formula (4). 【Chemistry 4】 (In formula (4), R ５０ ~R ５５ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, and an alkoxymethyl group. However, R ５０ ~R ５５ (At least one of these is a methylol group or an alkoxymethyl group.)

15. The resin composition according to claim 5 or 6, wherein the alkali-soluble resin (A) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof.

16. The resin composition according to claim 5 or 6, used for forming a pixel division layer in an organic EL display device.

17. A cured product obtained by curing the resin composition according to claim 5.

18. A cured product containing the compound described in claim 1.

19. A display device comprising the cured product according to claim 17 or 18.

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