WO2023013550A1

WO2023013550A1 - Compound, resin composition, cured product and display device

Info

Publication number: WO2023013550A1
Application number: PCT/JP2022/029311
Authority: WO
Inventors: 西岡拓紀; 小森悠佑; 三好一登
Original assignee: 東レ株式会社
Priority date: 2021-08-04
Filing date: 2022-07-29
Publication date: 2023-02-09
Also published as: KR20240045164A; JPWO2023013550A1

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

Compound, resin composition, cured product, and display device

The present invention relates to a compound, a resin composition, a cured product using the same, and a display device.

Cured products obtained by curing compositions containing polyimide and polybenzoxazole are widely used as insulating films, protective films, and planarizing films for semiconductor devices and display devices. Among them, when used in a display device, for example, in applications such as organic electroluminescence (Electroluminescence: hereinafter referred to as EL) display pixel division layer and liquid crystal display black matrix, the cured product is used to improve contrast. It is required to lower the light transmittance. In addition, in order to prevent deterioration, malfunction, leakage current, etc. due to light entering the driving thin film transistor (hereinafter referred to as TFT) of the display device, the pixel division layer of the organic EL display and the TFT of the organic EL display A planarizing film provided on the substrate is also required to have a low transmittance.

As a technique for reducing the light transmittance in the visible light region of 400 nm or more in the cured product, carbon black, organic / inorganic pigments, dyes, etc. are added to the resin composition, as seen in black matrix materials for liquid crystal displays and RGB paste materials. and a method of adding a coloring agent.

Techniques for reducing the light transmittance of a cured product in a resin composition include, for example, a method of adding a quinonediazide compound to an alkali-soluble resin, a dye soluble in both an alkaline developer and an organic solvent (see Patent Document 1), A method of adding a black oil-soluble dye to a photosensitive resin (see Patent Document 2), and adding at least one colorant selected from an esterified quinonediazide compound and a dye, an inorganic pigment, and an organic pigment to an alkali-soluble heat-resistant resin. (see Patent Document 3), and a method of adding a xanthene-based acid dye and a triarylmethane-based acid dye to a binder resin (see Patent Document 4).

JP-A-7-261015 JP-A-10-254129 Japanese Patent Application Laid-Open No. 2004-145320 JP 2013-50707 A

However, with these technologies, there was a problem that the film loss during alkali development was large due to the use of dyes, and the residual film rate was low.

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

(In formula (1), A ^n- is an n-valent anion represented by formula (2) or formula (3). R ¹ to R ⁴ each independently represent an alkyl group having 5 to 10 carbon atoms) where n is an integer from 1 to 3.)

(In formula (2), R ⁵ to R ⁸ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ⁹ to R ¹⁴ are , each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ¹⁵ to R ¹⁸ each independently represent 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 optionally substituted carbon atoms 1 to 20 R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.R ⁵ At least one of R ⁸ and R ¹⁵ to R ¹⁸ 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 ^— .)

(In Formula (3), R ²⁷ to R ³⁰ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ³¹ to R ³⁶ are Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ³⁷ to R ⁴¹ each independently represent a hydrogen atom, a halogen atom, —SO ₃ H, —SO ₃ ^— , —SO ₃ NR ⁴² R ⁴³ , -COOH, -COO ^- , -COOR ⁴⁴ , -CONR ⁴⁵ R ⁴⁶ , -OR ⁴⁷ , -NR ⁴⁸ R ⁴⁹ or 1 having 1 to 20 carbon atoms which may have a substituent represents a valent hydrocarbon group, adjacent ones among R ³⁷ to R ⁴¹ may be bonded to each other to form a cyclic structure, and R ⁴² to R ⁴⁹ each independently represent a hydrogen atom or represents an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein at least two of R ²⁷ to R ³⁰ and R ³⁷ to R ⁴¹ are —SO ₃ ^— or —COO ^— is a monovalent hydrocarbon group having 1 to 20 carbon atoms, —SO ₃ ^— or —COO ^— .)
[2] The compound according to [1] above, wherein in formula (1), all of R ¹ , R ² , R ³ and R ⁴ are the same substituent.
[3] The compound according to [1] or [2] above, wherein all of R ¹ , R ² , R ³ and R ⁴ in formula (1) are alkyl groups having 5 or 6 carbon atoms.
[4] The compound according to any one of [1] to [3] above, wherein the maximum absorption wavelength in the region of 350 nm or more and 700 nm or less is present in any of the region of 500 nm or more and 700 nm or less.
[5] A resin composition containing the compound according to any one of [1] to [4] above and (A) an alkali-soluble resin.
[6] In the above [5], wherein the mass ratio of the ammonium cation species in the formula (1) to the total mass of the organic cation species in the resin composition is 50% by mass or more and 100% by mass or less. The described resin composition.
[7] The compound according to any one of [1] to [4] above,
a compound having a maximum absorption wavelength in the range of 500 nm or more and less than 580 nm in the region of 350 nm or more and 700 nm or less;
7. The resin composition according to claim 5, comprising a compound having a maximum absorption wavelength in the range of 580 nm to 700 nm in the range of 350 nm to 700 nm.
[8] The above [5] to [7], wherein the total mass of all chlorine atoms and all bromine atoms contained in the resin composition is 150 mass ppm or less with respect to the total mass of the solid content of the resin composition. The resin composition according to any one of.
[9] The resin composition according to any one of [5] to [8] above, further comprising (B) a photosensitive compound.
[10] The resin composition according to [9] above, wherein the photosensitive compound (B) contains a quinonediazide compound.
[11] The quinonediazide compound contains a compound in which sulfonic acid of quinonediazide is ester-bonded to the hydroxy groups of the polyhydroxy compound, and 100 mol% of the hydroxy groups are ester-bonded to the sulfonic acid of quinonediazide. The resin composition according to [10] above, wherein the proportion of hydroxy groups is 50 mol% or more and 90 mol% or less.
[12] The resin composition according to any one of [5] to [11] above, further comprising (C) a thermochromic compound.
[13] The above [ 12].
[14] The (C) thermochromogenic 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 has the formula ( The resin composition according to [12] or [13] above, which contains a triazine ring-containing compound represented by 4).

(In formula (4), R ⁵⁰ to R ⁵⁵ are each independently 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, provided that at least one of R ⁵⁰ to R ⁵⁵ is a methylol group or an alkoxymethyl group.)
[15] The above [5], wherein the (A) alkali-soluble resin contains one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof. ] The resin composition according to any one of [14].
[16] The resin composition according to any one of [5] to [15] above, which is used for forming a pixel division layer of an organic EL display device.
[17] A cured product obtained by curing the resin composition according to any one of [5] to [16] above.
[18] A cured product containing the compound according to any one of [1] to [4] above.
[19] A display device comprising the cured product according to [17] or [18] above.

By using the compound of the present invention, it is possible to obtain a resin composition having a high residual film rate during alkali development.

1 is a schematic diagram of a substrate used in an organic EL display device; FIG.

The present invention will be described in detail below.

The compound of the present invention is a compound represented by formula (1). The compound represented by formula (1) consists of an anion portion represented by A ^n- and a cation portion represented by (R ¹ R ² R ³ R ⁴ N ⁺ ) _n .

In formula (1), A ^n- is an n-valent anion represented by formula (2) or formula (3).

In formula (2), R ⁵ to R ⁸ each independently represent 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 represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. R ¹⁵ to R ¹⁸ each independently represent 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 an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms; R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

Here, the optionally substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or the optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms has Substituents that may be used include halogen atoms, hydroxyl groups, alkoxy groups, phenoxy groups, carboxyl groups, sulfo groups, acyl groups, amino groups, imino groups, amide groups, imido groups, nitro groups, cyano groups, —SO ₃ ^— , Known substituents such as —COO ^— can be mentioned.

In formula (2), at least one of R ⁵ to R ⁸ and R ¹⁵ to R ¹⁸ 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 ^- . By satisfying these conditions, the structure represented by formula (2) becomes an anion.

As such anions, C.I. I. Acid Red 50, 52, 289; C.I. I. Examples include the anion portion of xanthene-based acid dyes such as Acid Violet 9 and 30.

In formula (3), R ²⁷ to R ³⁰ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ³¹ to R ³⁶ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. R ³⁷ to R ⁴¹ are each independently a hydrogen atom, a halogen atom, —SO ₃ H, —SO ₃ ^— , —SO ₃ NR ⁴² R ⁴³ , —COOH, —COO ^— , —COOR ⁴⁴ , —CONR ⁴⁵ R ⁴⁶ , -OR ⁴⁷ , -NR ⁴⁸ R ⁴⁹ or an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms; Adjacent ones among R ³⁷ to R ⁴¹ may be bonded to each other to form a cyclic structure. R ⁴² to R ⁴⁹ each independently represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

Here, among R ³⁷ to R ⁴¹ , mutually adjacent ones refer to groups existing at the ortho position of a substituent when a given group is focused on. For example, in R ³⁸ , R ³⁷ or R ³⁹ corresponds to R 38 and R ³⁸ adjacent to each other.

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

At least two of R ²⁷ to R ³⁰ and R ³⁷ to R ⁴¹ are monovalent hydrocarbon groups having 1 to 20 carbon atoms having -SO ₃ ^- or ^-COO- , -SO ₃ ^- or ^-COO- be. By satisfying this, the structure represented by Formula (3) becomes an anion.

As such anions, C.I. I. Acid Violet 15, 17, 19, 21, 38, 49, 72; C.I. I.

Acid Blue

1, 3, 7, 9, 15, 22, 83, 90, 93, 104, 108, 147; C.I. I.

Acid Green

3, 5, 6, 8, 9, 16, 50; C.I. I. The anion portion of triarylmethane-based acid dyes such as Food Green 3 and the like can be mentioned.

R ¹ to R ⁴ in the cation moiety are each independently an alkyl group having 5 to 10 carbon atoms. That is, the cation moiety is a quaternary ammonium cation having four alkyl groups each having 5 to 10 carbon atoms, each of which may be different. In formula (1), all of R ¹ , R ² , R ³ and R ⁴ are preferably the same substituent. That is, the cation moiety is preferably a quaternary ammonium cation having four identical alkyl groups of 5 to 10 carbon atoms. When all of R ¹ to R ⁴ are the same substituent, it is possible to improve the reliability of an organic EL display device having, as a pixel dividing layer, a cured product made of a resin composition containing the compound of the present invention, which will be described later. can. Examples of ammonium cations having four alkyl groups having 5 to 10 carbon atoms include tetrapentylammonium cations, tetrahexylammonium cations, tetraoctylammonium cations, tetradecylammonium cations, and the like. Among them, all of R ¹ , R ² , R ³ and R ⁴ in formula (1) are preferably alkyl groups having 5 or 6 carbon atoms, such as tetrapentylammonium cation (5 carbon atoms), tetrahexylammonium It preferably has a cation (6 carbon atoms) structure.

The compound represented by formula (1) is, for example, an aqueous solution of a salt containing an anion represented by formula (2) or formula (3) (hereinafter referred to as an anion component) and a salt containing the quaternary ammonium cation ( By preparing aqueous solutions of each component (hereinafter referred to as a cation component) and mixing the two with stirring, the compound is produced as a precipitate. Here, the counter cation contained in the anion component is not particularly limited, and examples thereof include sodium cations and potassium cations. Moreover, the counter anion contained in the cation component is not particularly limited, and examples thereof include chloride anions and bromide anions. The compound represented by the formula (1) can be obtained by collecting the generated precipitate by filtration. The obtained compound represented by formula (1) is preferably dried at about 60 to 70°C.

A compound represented by formula (1) can be identified by a known method. For example, the hydrogen nuclear magnetic resonance ( ¹ H NMR) spectrum of the compound represented by Formula (1) is a superposition of peaks derived from anions and cations that constitute the compound. These peaks can be distinguished by comparing the 1H NMR spectra of the anionic and cationic components, respectively. Among them, the triplet peak derived from the alkyl terminal (CH ₃ ) of the quaternary ammonium cation having four alkyl groups with 5 to 10 carbon atoms appears in the chemical shift value (δ) region of 0.5 to 1.0. . In particular, when the compound represented by formula (1) has four identical alkyl groups, the peak becomes a single triplet peak and the integrated value is 12×n.

The compound of the present invention preferably has a maximum absorption wavelength in the range of 350 nm or more and 700 nm or less in any of the range of 500 nm or more and 700 nm or less. When the maximum absorption wavelength of the compound of the present invention is within this range, the sensitivity of the photosensitive resin composition containing the compound of the present invention, which will be described later, can be improved.

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

The content of the compound represented by formula (1) in the resin composition is preferably 10 to 75 parts by mass, more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). When the content of the compound represented by Formula (1) is 10 parts by mass or more, the light of the corresponding wavelength can be sufficiently absorbed. Further, by setting the amount to 75 parts by mass or less, it is possible to reduce the residue at the opening.

In the resin composition of the present invention, the mass ratio of the ammonium cation species in the formula (1) to the total mass of the organic cation species is preferably 50% by mass or more and 100% by mass or less. When the mass ratio of the ammonium cation species is within this range, the storage stability of the resin composition of the present invention during frozen storage can be enhanced. The total mass of organic cationic species and the percentage mass of ammonium cationic species can be determined by cation chromatography.

In the resin composition of the present invention, the compound represented by formula (1) is a compound having a maximum absorption wavelength in the range of 500 nm or more and less than 580 nm in the range of 350 nm or more and 700 nm or less, and a compound having a maximum absorption wavelength in the range of 350 nm or more and 700 nm or less It is preferable to contain a compound having a maximum absorption wavelength in the range of 580 nm or more and 700 nm or less. By containing 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 (C) a thermochromic compound described later in combination.

Examples of compounds represented by formula (1) having a maximum absorption wavelength in the range of 500 nm or more and less than 580 nm in the region of 350 nm or more and 700 nm or less include C.I. I. Compounds having an anion moiety of Acid Red 52,289 and the like can be mentioned. Examples of the compound represented by formula (1) having a maximum absorption wavelength in the range of 580 nm to 700 nm in the range of 350 nm to 700 nm include C.I. I. Compounds having an anion portion of Acid Blue 83 and 90 are included.

In the resin composition of the present invention, the total mass of all chlorine atoms and all bromine atoms contained in the resin composition is preferably 150 mass ppm or less with respect to the total mass of solids in the resin composition. , 100 ppm by mass or less, and more preferably less than 2 ppm by mass, which is the detection limit of combustion ion chromatography. An organic EL display device having a cured product obtained by curing the resin composition by setting the total amount of all chlorine atoms and all bromine atoms contained in the resin composition to 150 mass ppm or less with respect to the solid content of the resin composition. deterioration of the electrodes and the light-emitting layer can be suppressed, and long-term reliability can be improved. The total mass of all chlorine atoms and all bromine atoms contained in the resin composition can be determined, for example, by burning the resin composition in a combustion tube of an analyzer, absorbing the generated gas into a solution, and subjecting a part of the absorption liquid to ion chromatography. It can be determined by combustion ion chromatography with graphical analysis.

<(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. More specifically, a silicon wafer is coated with a solution obtained by dissolving a resin in γ-butyrolactone, and prebaked at 120° C. for 4 minutes to form a prebaked film having a film thickness of 10 μm±0.5 μm. A resin having a dissolution rate of 50 nm/min or more, which is obtained from the film thickness reduction when immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 1° C. for 1 minute and then rinsed with pure water.

(A) The alkali-soluble resin preferably has an acidic group in the structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility. Preferred acidic groups include carboxyl groups, hydroxyl groups, sulfonic acid groups, and thiol groups.

(A) Specific examples of alkali-soluble resins include polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, phenolic resins, polymers composed of radically polymerizable monomers having alkali-soluble groups, siloxane polymers, and cyclic olefins. Polymers, cardo resins, and the like. (A) The alkali-soluble resin may contain two or more of these resins. (A) Alkali-soluble resin preferably contains one having high heat resistance. In addition, in order to obtain excellent properties as a flattening film, a pixel dividing layer, a partition wall, and a protective film used in organic light-emitting devices, display devices, and semiconductor elements, (A) the alkali-soluble resin has a temperature of 200° C. or higher after heat treatment. It is preferable to contain a material with a small amount of outgassing at a high temperature of . Specifically, (A) the alkali-soluble resin preferably contains one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof. .

Polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and their copolymers will be explained. Polyimide is not particularly limited as long as it has an imide ring, and polybenzoxazole is not particularly limited as long as it has a benzoxazole ring. The polyimide precursor is not particularly limited as long as it has a structure that becomes a polyimide having an imide ring by dehydration and ring closure. It is not particularly limited as long as it has a structure that becomes oxazole.

(A) Polyimides, polyimide precursors, polybenzoxazoles, and polybenzoxazole precursors are more preferably used as the alkali-soluble resin.

A polyimide has a structural unit represented by formula (5).

In formula (5), R ⁵⁶ represents a 4- to 10-valent organic group, and R ⁵⁷ represents a 2- to 10-valent organic group. R ⁵⁸ and R ⁵⁹ each independently represent a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group, or a substituent represented by formula (6) or formula (7). p represents an integer of 0 to 6, q represents an integer of 0 to 8, and p+q>0.

In formulas (6) and (7), R ⁶⁰ to R ⁶² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or represents an aryl group. The above alkyl group, acyl group and aryl group may be unsubstituted or substituted.

A polyimide precursor has a structural unit represented by formula (8).

In formula (8), R ⁶³ represents a 4- to 10-valent organic group, and R ⁶⁴ represents a 2- to 10-valent organic group. R ⁶⁵ represents a substituent represented by the formula (6) or formula (7), R ⁶⁶ represents a hydroxyl group, a sulfonic acid group, or a thiol group, R ⁶⁷ represents a hydroxyl group, a sulfonic acid group, a thiol group, or the formula ( 6) or a substituent represented by formula (7); r represents an integer of 2 to 8, s represents an integer of 0 to 6, t represents an integer of 0 to 8, and 2≦r+s≦8.

Polybenzoxazole has a structural unit represented by formula (9).

In formula (9), R ⁶⁸ represents a divalent to 10-valent organic group, and R ⁶⁹ represents a 4- to 10-valent organic group having an aromatic structure. R ⁷⁰ and R ⁷¹ each independently represent a hydroxyl group, a carboxy 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, v represents an integer from 0 to 6, and u+v>0.

A polybenzoxazole precursor has a structural unit represented by formula (10).

In formula (10), R ⁷² represents a divalent to 10-valent organic group having an aromatic structure, and R ⁷³ represents a 4- to 10-valent organic group. R ⁷⁴ represents a sulfonic acid group, a thiol group or a substituent represented by formula (6) or formula (7), R ⁷⁵ represents a hydroxyl group, carboxy group, sulfonic acid group, thiol group or formula (6) or formula ( represents a substituent represented by 7); w represents an integer of 2 to 8, x represents an integer of 0 to 8, y represents an integer of 0 to 6, and 2≦w+y≦8.

At least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof is the above formula (5), formula (8), formula (9) or formula It preferably has 5 to 100,000 structural units represented by (10). Further, one or more selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof is the above formula (5), formula (8), formula (9) Alternatively, it may have other structural units in addition to the structural units represented by formula (10). In this case, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof is the above formula (5), formula (8), formula (9) ) or formula (10) in an amount of 50 mol % or more, more preferably 70 mol % or more of the total number of structural units.

R ⁵⁶ -(R ⁵⁸ ) _p in formula (5) and (R ⁶⁵ ) _r -R ⁶³ -(R ⁶⁶ ) _s in formula (8) are residues of tetracarboxylic acid or derivatives thereof. show. Residues of tetracarboxylic acid derivatives include residues of tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid active diesters.

Examples of residues of tetracarboxylic acids or derivatives thereof 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(3,4-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 Acids and aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid, or their tetracarboxylic acid di Examples include residues such as anhydrides, tetracarboxylic acid dichlorides or tetracarboxylic acid activated diesters.

In the formula, R ⁷⁶ represents an oxygen atom, C(CF ₃ ) ₂ or C(CH ₃ ) ₂ . ^R77 and ^R78 each independently represent a hydrogen atom or a hydroxyl group.

R ⁶⁸ -(R ⁷⁰ ) _u in the formula (9) and R ⁷² -(R ⁷⁴ ) _x in the formula (10) each represent a residue of a dicarboxylic acid or a derivative thereof. Residues of dicarboxylic acid derivatives include residues of dicarboxylic anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.

Examples of dicarboxylic acid residues or residues of derivatives thereof include terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, etc., or , their dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, and the like. Examples of tricarboxylic acid residues or residues of derivatives thereof include trimellitic acid, trimesic acid, diphenylethertricarboxylic acid, biphenyltricarboxylic acid, etc., or tricarboxylic acid anhydrides, tricarboxylic acid chlorides, and tricarboxylic acids thereof. Examples include residues such as active esters.

R ⁵⁷ -(R ⁵⁹ ) _q in formula (5) and R ⁶⁴ -(R ⁶⁷ ) _t in formula (8) represent a residue of diamine or a derivative thereof.
Further, R ⁶⁹ -(R ⁷¹ ) _v in formula (9) and (OH) _w -R ⁷³ -(R ⁷⁵ ) _y in formula (10) are bisaminophenol compounds or derivative residues thereof among diamines. represents Diamine and bisaminophenol derivatives include diisocyanate compounds or trimethylsilylated diamines.

Examples of residues of diamines and bisaminophenol compounds or residues of derivatives thereof include 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diamino diphenylmethane, 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'-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 a portion of the hydrogen atoms of these aromatic rings are substituted with alkyl groups, hydroxyl groups or halogen atoms, and aliphatic Examples include cyclohexyldiamine, methylenebiscyclohexylamine, and residues of diamines having the structures shown below. You may use 2 or more types of these.

In the formula, R ⁷⁶ represents an oxygen atom, C(CF ₃ ) ₂ or C(CH ₃ ) ₂ . R ⁷⁷ to R ⁸⁰ each independently represent a hydrogen atom or a hydroxyl group.

In addition, by blocking the terminal of these alkali-soluble resins with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having an acidic group, an alkali-soluble resin having an acidic group at the main chain terminal can be obtained. .

Preferred examples of such monoamines having an acidic group 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, 4-aminothiophenol and the like. You may use 2 or more types of these.

Preferred examples of such acid anhydrides, acid chlorides and monocarboxylic acids include acids such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride and 3-hydroxyphthalic anhydride. Monocarboxylic acids such as anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, monoacid chloride compounds in which the carboxyl groups of these are acid chlorides, monoacid chloride compounds and N -hydroxybenzotriazole and active ester compounds obtained by reaction with N-hydroxy-5-norbornene-2,3-dicarboximide. You may use 2 or more types of these.

The (A) alkali-soluble resin used in the resin composition is synthesized by a known method. In the case of polyimide precursors such as polyamic acid and polyamic acid esters, the production methods include, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, and a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol. , then a method of reacting with an amine in the presence of a condensing agent, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine. .

In the case of polyimide, it can be obtained, for example, by subjecting the polyamic acid or polyamic acid ester obtained by the method described above to dehydration and ring closure by heating or chemical treatment with an acid or base.

In the case of a polybenzoxazole precursor, such as polyhydroxyamide, it can be obtained by a condensation reaction between a bisaminophenol compound and a dicarboxylic acid. Specifically, a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding a bisaminophenol compound thereto, or a method of adding a tertiary amine such as pyridine to a solution of a bisaminophenol compound and dicarboxylic acid. For example, a solution of dichloride is added dropwise.

In the case of polybenzoxazole, it can be obtained, for example, by dehydrating and ring-closing the polyhydroxyamide or the like obtained by the above-described method by heating or chemical treatment with an acid or base.

(A) The content of the alkali-soluble resin is the resin composition 100 from the viewpoint of obtaining excellent properties as planarizing films, pixel dividing layers, partition walls, and protective films used in organic light-emitting devices, display devices, and semiconductor elements. It is preferably contained in an amount of 0.5% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less.

<(B) Photosensitive compound>
The resin composition of the present invention preferably further contains (B) a photosensitive compound. (B) By containing a photosensitive compound, the resin composition can be made into a photosensitive resin composition and patterned by photolithography. (B) Photosensitive compounds include photoacid generators and photopolymerization initiators. From the viewpoint of resolution, the photosensitive compound preferably contains a photoacid generator.

A quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, an iodonium salt, and the like can be contained as the photoacid generator. (B) The photosensitive compound preferably contains a quinonediazide compound. The quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is sulfonamide-bonded, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and/or sulfonamide. and the like. Among them, a polyhydroxy compound in which a sulfonic acid of quinonediazide is ester-bonded is preferable. In particular, in the resin composition of the present invention, the quinonediazide compound contains a compound in which the sulfonic acid of quinonediazide is ester-bonded to the hydroxy groups of the polyhydroxy compound, and the sulfonic acid of quinonediazide is It is more preferable that the ratio of hydroxy groups ester-bonded with is 50 mol % or more and 90 mol % or less. By containing a quinonediazide compound substituted by 50 mol % or more, the affinity of the quinonediazide compound to an alkaline aqueous solution is reduced, and the solubility of the unexposed area of the resin composition in an alkaline aqueous solution is greatly reduced. The sulfonyl group is changed to indenecarboxylic acid, and a high dissolution rate in an alkaline aqueous solution of the resin composition in the exposed area can be obtained. A pattern can be obtained with resolution. In addition, by containing the quinonediazide compound substituted by 90 mol % or less, it is possible to suppress the residue in the pattern openings. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm) and g-line (436 nm) of a general mercury lamp. Further, the photoacid generators may be used alone or in combination of two or more, and a highly sensitive photosensitive resin composition can be obtained.

As for quinonediazide, both a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group are preferably used. A 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure and full-wavelength exposure. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength. Further, a naphthoquinonediazidesulfonyl ester compound can be obtained by using a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule together, or a 4-naphthoquinonediazidesulfonyl ester compound and a 5-naphthoquinonediazidesulfonyl ester compound. can also be used together.

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

(B) The content of the photosensitive compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 100 parts by mass or less, more preferably with respect to 100 parts by mass of the alkali-soluble resin (A). is 80 parts by mass or less. If it is 1 to 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.

<(C) Thermochromic compound>
The resin composition of the present invention preferably further contains (C) a thermochromic compound. (C) The thermochromic compound does not have a maximum absorption wavelength in the region of 350 nm or more and 700 nm or less before heating, and generates a maximum absorption wavelength in any of the regions of 350 nm or more and 700 nm or less by heating at 120 ° C. or more (hereinafter , sometimes referred to as “thermocoloring”). (C) The thermochromogenic compound preferably contains a compound that, when heated at 120° C. or higher, produces a maximum absorption wavelength in any of the regions of 350 nm to 700 nm and 350 nm to 500 nm. By using such a thermochromic compound (C), the transmittance at 350 nm to 500 nm can be greatly reduced after heating at 120° C. or higher, and a cured product with a higher degree of blackness can be obtained.

(C) The thermochromic compound is preferably a thermochromic compound that thermally develops color at a temperature higher than 180°C. The higher the temperature at which the thermochromic compound thermally develops color, the better the heat resistance under high temperature conditions, and the less the color fades due to prolonged irradiation with ultraviolet light and visible light, and the better the light resistance.

(C) The thermochromogenic compound may be a general heat-sensitive dye or pressure-sensitive dye, or may be another compound. These thermochromic compounds are those that develop color by changing their chemical structure and charge state due to the action of acidic groups coexisting in the system during heat treatment at 120 ° C. or higher, or those that develop color by the presence of oxygen in the air. Examples include those that cause a thermal oxidation reaction or the like to develop a thermal color. Examples of the skeleton structure of the thermochromic compound include a triarylmethane skeleton, a diarylmethane skeleton, a fluorane skeleton, a bislactone skeleton, a phthalide skeleton, a xanthene skeleton, a rhodamine lactam skeleton, a fluorene skeleton, a phenothiazine skeleton, a phenoxazine skeleton, and a spiropyran skeleton. be done. Specific examples include the compounds described in JP-A-2004-326094. Among them, a hydroxyl group-containing compound having a triarylmethane skeleton is particularly preferable because of its high heat color development temperature and excellent heat resistance. These may be contained singly or in combination.

In addition, (C) the thermochromogenic 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, the formula (4) It is also preferable to contain a triazine ring-containing compound represented by.

In formula (4), R ⁵⁰ to R ⁵⁵ are each independently 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, It represents a methylol group and an alkoxymethyl group having 2 to 10 carbon atoms. At least one of R ⁵⁰ to R ⁵⁵ is a methylol group or an alkoxymethyl group having 2 to 10 carbon atoms.
By containing these compounds, the resin composition of the present invention develops color by heating regardless of the atmosphere during curing, and can reduce the transmittance of 300 nm to 500 nm after curing.

Aromatic hydrocarbons having at least one aromatic C—H bond and three phenolic hydroxyl groups in one aromatic ring include, for example, 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, 2,3,4,4′-tetrahydroxybenzophenone and the like. Further, aromatic hydrocarbons having at least one aromatic C—H bond and four or more phenolic hydroxyl groups in one aromatic ring include 1,2,3,4-tetrahydroxybenzene, 1,2, 3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, leucoquinizarin and the like. Among them, from the viewpoint of further lowering the transmittance of 300 nm to 500 nm after curing, at least one substitution position of the other phenolic hydroxyl group for one of the phenolic hydroxyl groups is preferably the ortho or para position. It is more preferable that the Examples of the compound in which at least one substitution position of the other phenolic hydroxyl group with respect to any phenolic hydroxyl group is at the para position include 1,2.4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 1, 2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, leucoquinizarin and the like.

In the triazine ring-containing compound represented by formula (4), at least one of R ⁵⁰ to R ⁵⁵ has a methylol group or an alkoxymethyl group, and are 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. Alkoxymethyl groups include methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl groups.

The content of (C) the thermochromic compound used in the present invention is preferably 5 to 80 parts by mass, particularly preferably 10 to 60 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the content of (C) the thermochromic compound is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet-visible region can be reduced. Moreover, 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 can be reduced.

<Other coloring agents>
The resin composition of the present invention may contain other colorants. Such coloring agents include dyes, organic pigments, and inorganic pigments, and can be used according to the purpose.

The resin composition of the present invention includes a compound represented by formula (1), (A) an alkali-soluble resin, (B) a photosensitive compound, (C) a thermochromic compound, and other compounds other than colorants, such as heat Various known additives such as a cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver and a surfactant may be contained.

<Solvent>
The resin composition of the present invention may contain a solvent. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 - polar aprotic solvents such as imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyamide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene ethers such as 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. You may contain 2 or more types of these. The content of the solvent is preferably 100 parts by mass or more in order to dissolve the composition in 100 parts by mass of the alkali-soluble resin (A). Moreover, the content of the solvent is preferably 10000 parts by mass or less, more preferably 5000 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin, from the viewpoint of coating properties.

The resin composition of the present invention can be used for forming insulating films, protective films, flattening films, etc. of semiconductor elements and display devices. Among them, it is preferably used for forming a planarizing layer and a pixel dividing layer of an organic EL display device because it is excellent in high heat resistance and low outgassing property to a planarizing layer and a pixel dividing layer. From the point of view of improving the contrast, it is particularly preferable to be used for forming the pixel division layer of the organic EL display device.

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

A compound represented by formula (1), (A) an alkali-soluble resin, optionally (B) a photosensitive compound, (C) a thermochromic compound, and other coloring agents, which are components constituting the resin composition of the present invention. , a thermal cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver, a surfactant, a solvent, etc., to obtain a resin composition. It is preferable that the resin composition to be used in the method for producing a resin composition film of the present invention, which will be described later, contains a solvent to dissolve the respective components. In such a case, methods for promoting dissolution include heating and stirring. 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 25°C. Moreover, the order of dissolving each component is not particularly limited, and for example, a method of sequentially dissolving a compound having a low solubility in a solvent may be used. 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 the mixture is stirred, it may be heated as necessary, and the temperature is usually from room temperature to 80°C. In addition, for ingredients that tend to generate air bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, dissolving the other ingredients before adding them at the end will prevent poor dissolution of other ingredients due to air bubbles. can be prevented.

The obtained resin composition is preferably filtered using a filtration filter to remove dust and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, and 0.02 μm. Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred. Moreover, when an organic pigment is contained in the resin composition, it is preferable to use a filtration filter having a pore size larger than the particle size of these pigments.

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

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

<Method for producing cured product>
An example of the method for producing the cured product of the present invention will be described.

In one example of a method for producing a cured product, (1) the above-described resin composition is applied to a substrate to form a coating film, (2) the coating film is exposed to actinic radiation, and the exposed coating (3) developing the exposed coating film with an alkaline solution to obtain a developed coating film; and (4) heating the developed coating film to obtain a cured product. have in this order.

(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., and the resin composition is coated. Get a coating of things. Prior to application, the substrate to be coated with the resin composition may be pretreated with the above-described adhesion improver. For example, a solution obtained by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate is used. and a method of treating the substrate surface. Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, vapor treatment, and the like. In the step of drying the coating film, the formed coating film is optionally dried under reduced pressure, and then using a hot plate, oven, infrared rays, etc., in the range of 50 ° C. to 180 ° C. for 1 minute to several hours. A coating film is obtained by applying the heat treatment of.

Next, (2) the step of exposing the coating film will be described.
The coating film is irradiated with actinic radiation (hereinafter sometimes referred to as exposure). At this time, if necessary, the exposure may be performed through a photomask having a desired pattern, or the coating film may be exposed directly with a laser or the like. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc. In the present invention, i-rays (365 nm), h-rays (405 nm) and g-rays (436 nm) of mercury lamps can be used. preferable.

Next, (3) the step of developing the exposed coating film with an alkaline solution to obtain a developed coating film will be described.
The exposed coating film is developed using an alkaline solution to remove the exposed portion of the coating film. The developer at this time is tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol. , dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and other alkaline compounds. In some cases, these alkaline aqueous solutions are added with a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, One or more of alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added. As a developing method, methods such as spray, puddle, immersion, and ultrasonic waves are possible.

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

Next, (4) the step of heat-treating the developed coating film to obtain a cured product will be described.
By heat-treating the developed coating film, the residual solvent and components with low heat resistance can be removed, so that the heat resistance and chemical resistance of the cured product can be improved. For this heat treatment, a certain temperature is selected and the temperature is raised stepwise, or a certain temperature range is selected and the temperature is raised continuously for 5 minutes to 5 hours. For example, a method of heat-treating at 230° C. for 60 minutes can be used. The heat treatment conditions in the present invention are preferably 200° C. or higher, more preferably 230° C. or higher. The heat treatment conditions are preferably 400° C. or lower, more preferably 350° C. or lower.

<Display device>
The display device of the present invention comprises the cured product of the present invention.
A cured product obtained by curing the resin composition is a substrate on which TFTs are formed, a flattening layer on the driving circuit, a pixel dividing layer and a display element on the first electrode, and a flattening layer of a display device having the second electrode in this order. and the pixel division layer. Examples of display devices having such a configuration include liquid crystal display devices and organic EL display devices. Among them, the pixel division layer is particularly suitable for use in organic EL display devices in which high heat resistance and low outgassing properties are required for the planarization layer and the pixel division layer, and can improve the contrast of the organic EL display device. is particularly preferably used for

A cured product obtained by curing the resin composition of the present invention may be used for either one of the flattening layer and the pixel dividing layer, or may be used for both. An active matrix type display device has a TFT and wirings located on the sides of the TFT and connected to the TFT on a substrate such as glass, and has a flattening layer thereon so as to cover unevenness. Furthermore, a display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer.

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

<Evaluation of residual film ratio>
The resin compositions prepared in Examples and Comparative Examples (hereinafter also referred to as varnish) were spun onto a glass substrate (manufactured by Geomatec Co., Ltd.; hereinafter referred to as "ITO substrate") on which an ITO film was formed by sputtering. It was applied by spin coating using a coater (MS-A100; manufactured by Mikasa) so that the film thickness after heat treatment (cure) was 3.0 μm, and a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE) was used. was prebaked at 120° C. for 120 seconds to prepare a prebaked film. The resulting prebaked film was developed with a 2.38% by mass tetramethylammonium (TMAH) aqueous solution for 60 seconds to obtain a desired film thickness, and then rinsed with pure water to obtain a developed film.

The film thicknesses of the pre-baked film and the developed film at the center of the substrate are measured using a stylus profiler (P-15; manufactured by KLA-Tencor Co., Ltd.). determined as follows.
Remaining film ratio [%] = (film thickness of developed film)/(film thickness of prebaked film) x 100
A: Remaining film rate is 80% or more and 100% or less B: Remaining film rate is 50% or more and less than 80% C: Remaining film rate is less than 50%.

(2) Evaluation of changes in opening dimensions The sensitivity of the pre-baked film obtained by the above procedure was measured using a ghi-line mask aligner (PEM-6M; manufactured by Union Optical Co., Ltd.) at an exposure amount of 0 to 1000 mJ/cm ^{2 .} (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International). After the exposure, the film was developed with a 2.38 mass % tetramethylammonium (TMAH) aqueous solution for 60 seconds to obtain a desired film thickness, and then rinsed with pure water to obtain a relief pattern. Observed at a magnification of 100 using an FDP microscope MX61 (manufactured by Olympus Corporation), aperture size (aperture size after development) at an exposure amount that forms a 20 μm line-and-space pattern with a width of 1:1. was measured. After that, the resulting pattern was cured in an oven at 230° C. for 60 minutes in a nitrogen atmosphere, and the opening size (opening size after curing) was measured at the same exposure dose as above. From these measured values, the change in opening dimension was obtained by the following formula and judged as follows.
Aperture dimension change [μm] = (aperture dimension after development) - (aperture dimension after curing)
A: Change in opening dimension is 0.0 μm or more and 0.1 μm or less B: Change in opening dimension is more than 0.1 μm and not more than 0.2 μm C: Change in opening dimension is more than 0.2 μm or less than 0.0 μm.

(3) Evaluation of Reliability Reliability was evaluated based on the emission area ratio of an organic EL display device having, as a pixel dividing layer, a cured product made of the resin composition prepared in Examples and Comparative Examples.

Schematic diagrams of the substrates used are shown in FIGS. First, on an alkali-free glass substrate 1 of 38×46 mm, an ITO transparent conductive film of 10 nm was formed on the entire surface of the substrate by a sputtering method and etched as a first electrode 2 . At the same time, an auxiliary electrode 3 was also formed in order to take out the second electrode (FIG. 1(a)). The obtained substrate was ultrasonically cleaned for 10 minutes with "Semicoclean" (registered trademark) 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then cleaned with ultrapure water. Next, the entire surface of the substrate was coated with the photosensitive resin composition prepared in each example and comparative example by spin coating, and prebaked on a hot plate at 100° C. for 2 minutes. After the film was exposed to UV light through a photomask, it was developed with a 2.38 mass % tetramethylammonium hydroxide aqueous solution to dissolve only the exposed portion, and then rinsed with pure water. The resulting pattern was cured in an oven at 230° C. for 60 minutes under a nitrogen atmosphere. In this manner, the pixel division layer 4 having a width of 70 μm and a length of 260 μm is arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposes the first electrode. It is formed only in the effective area of the substrate (FIG. 1(b)). Note that this opening finally becomes a light-emitting pixel. The effective area of the substrate was 16 mm square, and the thickness of the insulating layer was about 1.0 μm.

Next, using the substrate on which the first electrode 2, the auxiliary electrode 3 and the pixel dividing layer 4 were formed, an organic EL display device was produced. After performing a nitrogen plasma treatment as a pretreatment, an organic EL layer 5 including a light-emitting layer was formed by a vacuum deposition method (FIG. 1(c)). The degree of vacuum during vapor deposition was 1×10 ⁻³ Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition. First, 10 nm of compound (HT-1) was deposited as a hole injection layer, and 50 nm of compound (HT-2) was deposited as a hole transport layer. Next, a compound (GH-1) as a host material and a 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%. Next, compounds (ET-1) and (LiQ) as electron-transporting materials were laminated at a volume ratio of 1:1 to a thickness of 40 nm. Structures of compounds used in the organic EL layer are shown below.

Next, after vapor-depositing a compound (LiQ) to a thickness of 2 nm, MgAg was co-deposited to a thickness of 10 nm at a volume ratio of Mg and Ag of 10:1 to form the second electrode 6 (Fig. 1(d)). Finally, in a low-humidity nitrogen atmosphere, a cap-shaped glass plate was adhered using an epoxy resin adhesive for sealing, and four 5 mm square light emitting devices were fabricated on one substrate. Incidentally, the film thickness referred to here is the value displayed by the crystal oscillation type film thickness monitor.

The produced organic EL display device was driven to emit light by direct current driving at 10 mA/cm ² , and the light emitting area in the light emitting pixel (light emitting area before UV light irradiation) was measured. Next, it was placed on a hot plate heated to 80° C. with the light-emitting surface facing up, and irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 mW/cm ² . After 1000 hours, light was emitted by direct current driving at 10 mA/cm ² , and the light-emitting area in the light-emitting pixel (light-emitting area after UV light irradiation) was measured. From these measured values, the emission area ratio was determined by the following formula, and the reliability was determined as follows from the value.
Luminescent area ratio [%] = (luminous area after UV light irradiation) / (luminous area before UV light irradiation) x 100
A: Emission area ratio of more than 75% and 100% or less B: Emission area ratio of more than 50% and 75% or less C: Emission area ratio of 50% or less.

(4) Evaluation of frozen storage stability of the resin composition Each varnish was stored statically in a freezer at -18 ° C. for 60 days after filtration using a coating / developing device "CLEAN TRACK ACT-12" manufactured by Tokyo Electron Co., Ltd. was applied onto a 12-inch Si wafer and dried on a hot plate at 100° C. for 3 minutes to obtain a photosensitive resin film with a thickness of 1000 nm. For the obtained photosensitive resin film, the number of foreign substances having a size of 0.27 μm or more was counted using a wafer surface inspection device “WM-10” manufactured by Topcon Corporation. The measurement area was about 201 cm ² inside a circle with a radius of 8 cm from the center of the wafer, and the number of foreign substances (defect density) per 1 cm ² of the coating film was determined. "A" when the defect density per substrate is less than 1.00/cm ² , "B" when it is 1.00/cm ² or more and less than 3.00/cm ² , When it was 3.00/cm ² or more, it was judged as "C".

[Synthesis Example 1]
C.I. as an anion component was added to a separable flask. I. 20.3 g (0.035 mol) of Acid Red 52 and 400 g of pure water were added and stirred at room temperature for 30 minutes. An aqueous solution prepared by dissolving 16.9 g (0.039 mol) of tetrahexylammonium bromide as a cationic component in 1700 g of pure water was added thereto, followed by stirring at room temperature for 60 minutes. After that, the reaction solution was filtered to obtain a red solid. This solid was dried at 60° C. for 8 hours under reduced pressure to obtain compound z-1 represented by formula (1). The obtained compound was identified by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) (JNM-ECZ400R; manufactured by JEOL Ltd.).

¹ H NMR (400 MHz, DMSO-d ₆ ) δ: 8.26 (d, J = 2.0 Hz, 1H, ArH), 7.72 (dd, _J = 8.0 Hz, J = _2.0 Hz, 1H, ArH), 7.14 (d, J=8.0 Hz, 1H, ArH), 7.03 (s, 4H, ArH), 6.92 (s, 2H, ArH), 3.66-3. 61 (m, 8H, ArNCH ₂ ), 3.18-3.13 (m, 8H, NCH ₂ ), 1.56 (br, 8H, NCH ₂ CH ₂ ), 1.29 (br, 24H, N( _CH2 ) ₂ ₍ _CH2 ) ₃ ), 1.21 (t, J = 6.8 Hz, 12H, _ArNCH2CH3 ), 0.88 (t, J = 7.0 Hz, 12H, N( _CH2 ) _5CH3 ₎ .

[Synthesis Example 2]
In Synthesis Example 1, the formula ( A compound z-2 represented by 1) was obtained. The identification results are shown below.

¹ H NMR (400 MHz, DMSO-d ₆ ): 8.26 (d, J = 2.0 Hz, 1 H, ArH), 7.72 (dd, J = 8.0 Hz, J = 2.0 Hz, 1 H, 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, ArNCH ₂ ), 3.18-3.14 (m, 8H, NCH ₂ ), 1.61-1.54 (m, 8H, NCH ₂ CH ₂ ), 1.38-1.15 (m , 28H), 0.89 (t _, J=7.0 Hz, 12H, N( _CH2 ) _4CH3 ).

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

¹ H NMR (400 MHz, DMSO-d ₆ ): 9.92 (s, 2H, ArNH), 8.04-7.18 (m, 14H, ArH), 6.01 (s, 2H, ArH), 3 .18-3.13 (m, 8H, NCH ₂ ), 2.20-2.15 (m, 6H, ArCH ₃ ), 1.56 (br, 8H, NCH ₂ CH ₂ ), 1.29 (br , 24H, N( _CH2 ) ₂ ( _CH2 ) ₃ ) _, 0.88 (t, J=7.0 Hz, 12H, N( _CH2 ) _5CH3 ).

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

¹ H NMR (400 MHz, DMSO-d ₆ ): 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 ), 3.15 (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} ₎ _.

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

¹ H NMR (400 MHz, DMSO-d ₆ ): ¹ H NMR (400 MHz, DMSO-d ₆ ): 10.03 (s, 1 H, 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, ArCH ₂ N), 4.04 (m, 2H , ArOCH ₂ ), 3.68-3.62 (m, 4H, ArNCH ₂ ), 3.18-3.14 (m, 8H, NCH ₂ ), 1.79 (br s, 6H, ArCH ₃ ), 1.61-1.54 (m, 8H, NCH ₂ CH ₂ ), 1.39-1.19 (m, 33H), 0.89 (t, J=7.0 Hz, 12H, N(CH ₂ ) ₄ _CH3 ).

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

¹ H NMR (400 MHz, DMSO-d ₆ ): 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, ArNCH ₂ ), 3.15 (m, 8H, NCH ₂ ), 1.56 (br, 8H, NCH ₂ CH ₂ ), 1.35-1.22 (m , 25H), 0.88 (t _, J=7.0 Hz, 12H, N( _CH2 ) _5CH3 ).

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

¹ H NMR (400 MHz, DMSO- _d6 ): 8.19 (d, J = 1.6 Hz, 1 H, ArH), 7.62 (dd, _J = 8.0 Hz, J = _1.6 Hz, 1 H , ArH), 7.29 (d, J = 9.2 Hz, 4H, ArH), 6.98-6.91 (m, 5H, ArH), 3.62 (q, J = 6.9 Hz, ArNCH ₂ ), 3.15(m, 8H, _NCH2 ), 1.56(br, 8H, _NCH2CH2 ), 1.29(br, 24H, N( _CH2 ₎ ₂ ( _CH2 ) ₃ ), 1 .20 (t, J=7.0 Hz, 12H, _ArNCH2CH3 ), 0.88 (t _, J=7.0 Hz, 12H, N( _CH2 ) _5CH3 ₎ .

[Synthesis Example 8]
In the same manner as in Synthesis Example 1, compound z -8 was obtained. The identification results are shown below.

¹ H NMR (400 MHz, DMSO-d ₆ ): 8.26 (d, J = 2.0 Hz, 1 H, ArH), 7.72 (dd, J = 8.0 Hz, J = 2.0 Hz, 1 H, 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, ArNCH ₂ ), 3.18-3.14 (m, 8H, NCH ₂ ), 1.61-1.54 (m, 8H, NCH ₂ CH ₂ ), 1.38-1.15 (m , 68H), 0.86 (t _, J=7.0 Hz, 12H, N( _CH2 ) _9CH3 ).

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

¹ H NMR (400 MHz, DMSO-d ₆ ): 8.26 (d, J = 2.0 Hz, 1 H, ArH), 7.72 (dd, J = 8.0 Hz, J = 2.0 Hz, 1 H, 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, ArNCH ₂ ), 3.18-3.14 (m, 8H), 1.61-1.54 (m, 8H), 1.38-1.15 (m, 38H), 0.91- 0.84 (m, 12H).

[Synthesis Example 10]
In the same manner as in Synthesis Example 1, compound z -10 was obtained. The identification results are shown below.

¹ H NMR (400 MHz, DMSO-d ₆ ): 8.26 (d, J = 2.0 Hz, 1 H, ArH), 7.72 (dd, J = 8.0 Hz, J = 2.0 Hz, 1 H, 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, ArNCH ₂ ), 3.18-3.14 (m, 8H, NCH ₂ ), 1.61-1.54 (m, 8H, NCH ₂ CH ₂ ), 1.38-1.15 (m , 20H), 0.94 (t, J _{=7.0 Hz, 12H, N(CH2)3CH3} ₎ _.

[Synthesis Example 11]
In Synthesis Example 1, compound z-11 was obtained. The identification results are shown below.

¹ H NMR (400 MHz, DMSO- _d6 ): 8.26 (d, J = 2.0 Hz, 1 H, ArH), 7.72 (dd, _J = 8.0 Hz, J = _2.0 Hz, 1 H , ArH), 7.14 (d, J = 8.0 Hz, 1H, ArH), 7.03 (s, 4H, ArH), 6.92 (s, 2H, ArH), 3.66-3.61 (m, 8H, ArNCH ₂ ), 3.27-3.22 (m, 2H, NCH ₂ ), 3.02 (s, 9H, NCH ₃ ), 1.70-1.62 (m, 2H, NCH ₂ CH ₂ ), 1.27-1.19 (m, 38H), 0.85 (t, J=7.0 Hz, 3H, N(CH ₂ ) ₁₅ CH ₃ ).

Table 1 shows the anion components and cation components used in Synthesis Examples 1-11.

[Synthesis Example 12]
2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) 18.31 g (0.05 mol), propylene oxide 17.4 g (0.3 mol), and acetone 100 mL are placed in a three-necked flask. Weighed and dissolved. A solution of 20.41 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 10 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration 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 here with a balloon and reacted at room temperature for 2 hours. After 2 hours, it was confirmed that the balloon had not deflated any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by distillation under reduced pressure to obtain a hydroxy group-containing diamine compound (HA) having the following structure.

Under a dry nitrogen stream, 15.1 g (0.025 mol) of HA, 3.66 g (0.01 mol) of BAHF and 0.62 g (0.01 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) .0025 mol) was dissolved in 200 g of N-methylpyrrolidone (NMP). 22.2 g (0.05 mol) of 2,2-(3,4-dicarboxyphenyl)hexafluoropropane (hereinafter referred to as 6FDA) was added together with 50 g of NMP, and the mixture was stirred at 40° C. for 1 hour. After that, 2.73 g (0.025 mol) of 3-aminophenol (hereinafter referred to as MAP) was added and stirred at 40° C. for 1 hour. Further, a solution prepared by diluting 11.9 g (0.1 mol) of N,N-dimethylformamide dimethylacetal (hereinafter referred to as DFA) with 5 g of NMP was added, and the mixture was stirred at 40° C. for 2 hours. After stirring was completed, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. Further, it was 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.

[Synthesis Example 13]
21.2 g (0.05 mol) of 4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) under dry nitrogen stream and 26.8 g (0.1 mol) of 5-naphthoquinonediazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and allowed to cool to room temperature. 12.7 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the inside of the system did not reach 35° C. or higher. After dropping, the mixture was stirred at 40°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. After that, the deposited precipitate was collected by filtration and washed with 1 L of 1% aqueous hydrochloric acid. After that, it was washed twice with 2 L of water. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound b-1 represented by the following formula.

The compounds shown in each example and comparative example are shown below.

[Example 1]
Under yellow light, the compound z-1 obtained in Synthesis Example 1 as the compound represented by formula (1), (A) the polyimide precursor resin a-1 obtained in Synthesis Example 12 as an alkali-soluble resin, (B) photosensitive compound b-1 obtained in Synthesis Example 13 as a chemical compound, compound c-1 as a thermochromic compound (C), thermal cross-linking agent d-1 as other additives, γ-butyrolactone (GBL) and ethyl lactate as a solvent ( EL) was added in the amount shown in Table 1 and dissolved by stirring to prepare composition 1.

For composition 1, we evaluated the residual film ratio, change in opening size, and reliability.

[Examples 2 to 11, Comparative Examples 1 to 3]
Compositions 2 to 14 were prepared according to the compositions shown in Table 2 in the same manner as in Example 1.
Compositions 2-14 were evaluated in the same manner as in Example 1.

[Examples 12 and 13]
Compositions 1 and 11 were evaluated for frozen storage stability.

Tables 2 and 3 show the compositions and evaluation results of the resin compositions of Examples and Comparative Examples.

Compositions 12 to 14, which did not contain the compound represented by formula (1), had a low residual film rate. It was confirmed that the resin composition containing the compound represented by the formula (1) of the present invention has a high residual film rate.

The compound, resin composition, and cured product of the present invention can be used as a surface protective film of a semiconductor device, an interlayer insulating film, a pixel division layer of an organic EEL device, a flattening film of a driving TFT substrate of a display device using an organic EL device, It is suitably used for wiring protective insulating films for circuit boards, on-chip microlenses for solid-state imaging devices, flattening films for various displays and solid-state imaging devices, and solder resists for circuit boards.

1: glass substrate 2: first electrode 3: auxiliary electrode 4: pixel division layer 5: organic EL layer 6: second electrode

Claims

A compound represented by formula (1).

(In formula (1), A n- is an n-valent anion represented by formula (2) or formula (3). R 1 to R 4 each independently represent an alkyl group having 5 to 10 carbon atoms) where n is an integer from 1 to 3.)

(In formula (2), R 5 to R 8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R 9 to R 14 are , each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R 15 to R 18 each independently represent 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 optionally substituted carbon atoms 1 to 20 R 19 to R 26 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.R 5 At least one of R 8 and R 15 to R 18 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 — .)

(In Formula (3), R 27 to R 30 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R 31 to R 36 are Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R 37 to R 41 each independently represent a hydrogen atom, a halogen atom, —SO 3 H, —SO 3 — , —SO 3 NR 42 R 43 , -COOH, -COO - , -COOR 44 , -CONR 45 R 46 , -OR 47 , -NR 48 R 49 or 1 having 1 to 20 carbon atoms which may have a substituent represents a valent hydrocarbon group, adjacent ones among R 37 to R 41 may be bonded to each other to form a cyclic structure, and R 42 to R 49 each independently represent a hydrogen atom or represents an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein at least two of R 27 to R 30 and R 37 to R 41 are —SO 3 — or —COO — is a monovalent hydrocarbon group having 1 to 20 carbon atoms, —SO 3 — or —COO — .)
2. The compound according to claim 1, wherein in formula (1), R1 , R2 , R3 and R4 are all the same substituents.
3. The compound according to claim 1 or 2, wherein all of R1, R2 , R3 and R4 in formula (1) are alkyl groups having 5 or 6 carbon atoms.
3. The compound according to claim 1 or 2, wherein the maximum absorption wavelength in the range of 350 nm or more and 700 nm or less exists in any of the range of 500 nm or more and 700 nm or less.
A resin composition comprising the compound according to claim 1 and (A) an alkali-soluble resin.
The resin composition according to claim 5, wherein the mass ratio of the ammonium cation species in the formula (1) to the total mass of the organic cation species in the resin composition is 50% by mass or more and 100% by mass or less. thing.
A compound according to claim 1 or 2,
a compound having a maximum absorption wavelength in the range of 500 nm or more and less than 580 nm in the region of 350 nm or more and 700 nm or less;
7. The resin composition according to claim 5, comprising a compound having a maximum absorption wavelength in the range of 580 nm to 700 nm in the range of 350 nm to 700 nm.
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 mass ppm or less with respect to the total mass of solid content of the resin composition. .
7. The resin composition according to claim 5, further comprising (B) a photosensitive compound.
10. The resin composition according to claim 9, wherein (B) the photosensitive compound contains a quinonediazide compound.
The quinonediazide compound contains a compound in which the sulfonic acid of quinonediazide is ester-bonded to the hydroxy group of the polyhydroxy compound, and the hydroxy group ester-bonded to the sulfonic acid of quinonediazide accounts for 100 mol% of the total hydroxy groups. The resin composition according to claim 10, wherein the ratio is 50 mol% or more and 90 mol% or less.
7. The resin composition according to claim 5, further comprising (C) a thermochromic compound.
13. The method according to claim 12, wherein the (C) thermochromogenic compound contains a compound that, when heated at 120° C. or higher, exhibits a maximum absorption wavelength in the range of 350 nm or more and 700 nm or less and in the range of 350 nm or more and 500 nm or less. of the resin composition.
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 represented by formula (4) 13. The resin composition according to claim 12, containing the represented triazine ring-containing compound.

(In formula (4), R 50 to R 55 are each independently 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, provided that at least one of R 50 to R 55 is a methylol group or an alkoxymethyl group.)
7. The method according to claim 5 or 6, wherein the (A) alkali-soluble resin contains at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof. The described resin composition.
7. The resin composition according to claim 5, which is used for forming a pixel division layer of an organic EL display device.
A cured product obtained by curing the resin composition according to claim 5 .
A cured product containing the compound according to claim 1 .
A display device comprising the cured product according to claim 17 or 18.