CN116034318A

CN116034318A - Colored photosensitive resin composition, cured product, display device, and method for producing cured product

Info

Publication number: CN116034318A
Application number: CN202180056116.5A
Authority: CN
Inventors: 西冈拓纪; 小森悠佑; 三好一登
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2020-08-18
Filing date: 2021-08-05
Publication date: 2023-04-28
Also published as: TW202214745A; WO2022039034A1; JPWO2022039034A1; KR20230051765A

Abstract

The purpose of the present invention is to provide a colored photosensitive resin composition that can form a pattern while satisfying the characteristics of the residual film ratio, the opening residue, and the blackness. The present invention is a colored photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the (C) colorant contains (C1) a salt-forming compound containing an acid dye and a basic dye.

Description

Colored photosensitive resin composition, cured product, display device, and method for producing cured product

Technical Field

The present invention relates to a colored photosensitive resin composition, a cured product using the same, a display device, and a method for producing the cured product. More specifically, the present invention relates to cured products such as a surface protective film, an interlayer insulating film, a pixel dividing layer of an organic Electroluminescence (hereinafter referred to as EL) element, a planarizing film of a thin film transistor (Thin Film Transistor) substrate for driving a display device using an organic EL element, a wiring protective insulating film of a circuit board, an on-chip microlens (on-chip microlens) of a solid-state image pickup element, various planarizing films for a display/solid-state image pickup element, and a solder resist for a circuit board, which are suitable for a semiconductor element, and a colored photosensitive resin composition for forming the same.

Background

Cured products obtained by curing a composition containing polyimide or polybenzoxazole are widely used for semiconductor elements, insulating films for display devices, protective films, planarizing films, and the like. Among them, in the case of use in display devices, for example, in applications such as a pixel division layer of an organic EL display and a black matrix of a liquid crystal display, it is required to reduce the transmittance of a cured product to improve the contrast. In addition, in order to prevent deterioration, malfunction, leakage current, and the like due to light entering the driving TFT of the display device, it is also required to reduce transmittance for a pixel dividing layer of the organic EL display, a planarizing film provided on a TFT substrate of the organic EL display, and the like.

As a technique for reducing the transmittance of the cured product in the visible light range of 400nm or more, there is a method of adding a colorant such as carbon black, an organic/inorganic pigment, or a dye to a resin composition as seen in a black matrix material for a liquid crystal display or an RGB paste material.

As a technique for reducing the light transmittance of the cured product, there are, for example, the following positive photosensitive resin compositions: a method of adding a quinone diazide compound and a black pigment to a Novolac resin and/or an alkali-soluble resin containing a vinyl polymer (see patent document 1); a method of adding a photosensitive agent and a black pigment to a soluble polyimide (see patent document 2); a method of adding a quinone diazide compound and a pigment soluble in both an alkaline developer and an organic solvent to an alkali-soluble resin (see patent document 3); a method of adding a black oil-soluble dye to a photosensitive resin (see patent document 4); and a method of adding an esterified quinone diazide compound and at least one colorant selected from a dye, an inorganic pigment, an organic pigment to an alkali-soluble heat-resistant resin (see patent document 5); etc.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 6-230215

Patent document 2: japanese patent laid-open No. 2003-119381

Patent document 3: japanese patent laid-open No. 7-261015

Patent document 4: japanese patent laid-open No. 10-254129

Patent document 5: japanese patent application laid-open No. 2004-145320

Disclosure of Invention

Problems to be solved by the invention

However, the above-described technique has a problem that any of the characteristics of the film residue ratio, the opening residue, and the blackness is insufficient when patterning is performed.

Means for solving the problems

The invention relates to a colored photosensitive resin composition, which comprises (A) alkali-soluble resin, (B) photoacid generator and (C) colorant, wherein the (C) colorant comprises (C1) salifying compound containing acid dye and basic dye.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, the pattern processing can be performed while taking into consideration the characteristics of the film residue, the opening residue, and the blackness.

Drawings

Fig. 1 is a schematic view of a substrate used for an organic EL display device.

Detailed Description

The invention relates to a colored photosensitive resin composition, which comprises (A) alkali-soluble resin, (B) photoacid generator and (C) colorant, wherein the (C) colorant comprises (C1) salifying compound containing acid dye and basic dye. The present invention will be described in detail below.

Alkali-soluble resin (A)

The colored photosensitive resin composition of the present invention contains (A) an alkali-soluble resin. The alkali-soluble resin is a resin having a dissolution rate of 50 nm/min or more as defined below. Specifically, the following resins are meant: a solution obtained by dissolving a resin in gamma-butyrolactone is applied to a silicon wafer, prebaked at 120 ℃ for 4 minutes to form a prebaked film having a film thickness of 10 [ mu ] m + -0.5 [ mu ] m, the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 + -1 ℃ for 1 minute, and then rinsed with pure water, whereby the dissolution rate obtained from the film thickness reduction at this time is 50 nm/min or more.

In order to impart alkali solubility, (a) the alkali-soluble resin preferably has an acidic group in a structural unit of the resin and/or at a terminal of a main chain thereof. Preferable examples of the acidic group include a carboxyl group, a hydroxyl group, a sulfonic acid group, a thiol group, and the like.

Specific examples of the alkali-soluble resin (a) include polyimide, polyimide precursor, polybenzoxazole precursor, phenol resin, polymer formed from radical-polymerizable monomer having an alkali-soluble group, siloxane polymer, cyclic olefin polymer, and Cardo resin (Cardo resin). (A) The alkali-soluble resin may contain 2 or more of these resins. The alkali-soluble resin (A) preferably contains a resin having high heat resistance. In addition, in order to obtain excellent characteristics as a planarization film, a pixel dividing layer, a spacer, and a protective film used in an organic light-emitting device, a display device, and a semiconductor element, the alkali-soluble resin (a) preferably contains a resin having a small amount of exhaust gas at a high temperature of 200 ℃ or higher after heat treatment. Specifically, the alkali-soluble resin (a) preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof.

Polyimide, polyimide precursor, polybenzoxazole precursor and copolymers thereof are described. In the case of polyimide, polyimide having an imide ring may be used, and in the case of polybenzoxazole, polybenzoxazole having a benzoxazole ring may be used, and is not particularly limited. The polyimide precursor is not particularly limited as long as it has a structure in which a polyimide having an imide ring is formed by dehydration and ring closure, and the polybenzoxazole precursor is also not particularly limited as long as it has a structure in which a polybenzoxazole having a benzoxazole ring is formed by dehydration and ring closure.

The resin used as the alkali-soluble resin (a) is more preferably polyimide, a polyimide precursor, polybenzoxazole or a polybenzoxazole precursor.

The polyimide has a structural unit represented by the general formula (1).

[ chemical formula 1]

In the general formula (1), R ¹ R represents a 4-to 10-valent organic group having 5-40 carbon atoms ² Represents a 2-to 10-valent organic group having 5-40 carbon atoms. R is R ³ R is R ⁴ Each independently represents a hydroxyl group, a carboxyl group, a sulfonic group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3). p represents an integer of 0 to 6, q represents an integer of 0 to 8, and p+q > 0.

[ chemical formula 2]

In the general formula (2) and the general formula (3), R ⁵ ～R ⁷ Each 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, the acyl group, and the aryl group may be unsubstituted or substituted.

The polyimide precursor has a structural unit represented by the general formula (4).

[ chemical formula 3]

In the general formula (4),R ⁸ r represents a 4-to 10-valent organic group having 5-40 carbon atoms ⁹ Represents a 2-to 10-valent organic group having 5-40 carbon atoms. R is R ¹⁰ R represents a substituent represented by the above general formula (2) or general formula (3) ¹¹ Represents hydroxy, sulfo, thiol, R ¹² Represents a hydroxyl group, a sulfonic acid group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3). 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.ltoreq.r+s.ltoreq.8.

The polybenzoxazole has a structural unit represented by the general formula (5).

[ chemical formula 4]

In the general formula (5), R ¹³ R represents a 2-to 8-valent organic group having 5-40 carbon atoms ¹⁴ Represents a 4-to 10-valent organic group having 5-40 carbon atoms and an aromatic structure. R is R ¹⁵ R is R ¹⁶ Each independently represents a hydroxyl group, a carboxyl group, a sulfonic group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3). u represents an integer of 0 to 8, v represents an integer of 0 to 6, and u+v > 0.

The polybenzoxazole precursor has a structural unit represented by the general formula (6).

[ chemical formula 5]

In the general formula (6), R ¹⁷ Represents a 4-10 valent organic group having 5-40 carbon atoms and having an aromatic structure, R ¹⁸ Represents a 2-to 10-valent organic group having 5-40 carbon atoms. R is R ¹⁹ Represents a sulfonic acid group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3), R ²⁰ Represents a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3). 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.ltoreq.w+y.ltoreq.8.

More than 1 selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor and copolymers thereof preferably has 5 to 100,000 structural units represented by the above general formula (1), general formula (4), general formula (5) or general formula (6). In addition, 1 or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor and copolymers thereof may have other structural units in addition to the structural units represented by the general formula (1), the general formula (4), the general formula (5) or the general formula (6). In this case, 1 or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor and copolymers thereof preferably has 50mol% or more of the structural unit represented by the above general formula (1), general formula (4), general formula (5) or general formula (6) in the total number of structural units, more preferably 70mol% or more.

R in the general formula (1) ¹ -(R ³ ) _p And (R) in the general formula (4) ¹⁰ ) _r -R ⁸ -(R ¹¹ ) _s Represents the residue of a tetracarboxylic acid or a derivative thereof. The residue of the tetracarboxylic acid derivative may be a residue of tetracarboxylic dianhydride, tetracarboxylic acid dichloride or tetracarboxylic acid active diester.

Examples of the residue of the tetracarboxylic acid and its derivative include pyromellitic acid, 3',4' -biphenyltetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid, 2', 3' -biphenyltetracarboxylic acid, 3',4' -benzophenone tetracarboxylic acid, 2', aliphatic tetracarboxylic acid residues such as 3,3' -benzophenone tetracarboxylic acid, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane, 1-bis (3, 4-dicarboxyphenyl) ethane, 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-naphthalene tetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 2,3,5, 6-pyridine tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3, 4-cyclopentane tetracarboxylic acid, and the residues of tetracarboxylic acid, or the tetracarboxylic dianhydride, tetracarboxylic acid dichloride, tetracarboxylic acid active diester thereof.

[ chemical formula 6]

Wherein R is ²¹ Represents an oxygen atom, C (CF) ₃ ) ₂ Or C (CH) ₃ ) ₂ 。R ²² R is R ²³ Each independently represents a hydrogen atom or a hydroxyl group.

R in the above general formula (5) ¹³ -(R ¹⁵ ) _u And R in the general formula (6) ¹⁷ -(R ¹⁹ ) _x Represents the residue of a dicarboxylic acid or derivative thereof. Examples of the residue of the dicarboxylic acid derivative include a residue of a dicarboxylic acid anhydride, a dicarboxylic acid chloride, a dicarboxylic acid active ester, a tricarboxylic acid anhydride, a tricarboxylic acid chloride, a tricarboxylic acid active ester, and a dicarboxylic acid compound.

Examples of the residue of the dicarboxylic acid or derivative thereof include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyldicarboxylic acid, and the like, and the residue of a dicarboxylic anhydride, dicarboxylic acid chloride, or dicarboxylic acid active ester thereof. Examples of the residue of the tricarboxylic acid and its derivative include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyltricarboxylic acid, and the residue of tricarboxylic acid anhydride, tricarboxylic acid chloride, and tricarboxylic acid active ester thereof.

R in the general formula (1) ² -(R ⁴ ) _q And R in the general formula (4) ⁹ -(R ¹² ) _t Represents the residue of a diamine or derivative thereof.

In addition, R in the general formula (5) ¹⁴ -(R ¹⁶ ) _v And (OH) in the general formula (6) _w -R ¹⁸ -(R ²⁰ ) _y Represents a residue of a bisaminophenol compound or a derivative thereof. The residue of the bisaminophenol compound derivative may be a diisocyanate compound or trimethylsilylated diamine.

As the residue of the bisaminophenol compound and its derivatives, examples thereof include 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl methane, 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, and bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4,4 '-tetramethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 9-bis (4-aminophenyl) fluorene, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2 '-bis (trifluoromethyl) -3,3' -dihydroxybenzidine, 2 '-bis (trifluoromethyl) -5,5' -dihydroxybenzidine, or a compound obtained by substituting at least a part of hydrogen atoms of aromatic rings thereof with alkyl groups, hydroxyl groups or halogen atoms, aliphatic cyclohexyldiamine, and, methylene dicyclohexylamine, residues of diamines of the structure shown below, and the like. (A) The alkali-soluble resin may have two or more of these.

[ chemical formula 7]

Wherein R is ²¹ Represents an oxygen atom, C (CF) ₃ ) ₂ Or C (CH) ₃ ) ₂ 。R ²² ～R ²⁵ Each independently represents a hydrogen atom or a hydroxyl group.

In addition, by capping the terminal ends of these alkali-soluble resins with monoamines, anhydrides, acid chlorides, monocarboxylic acids having an acidic group, alkali-soluble resins having an acidic group at the terminal end of the main chain can be obtained.

Preferable examples of the monoamine having an acidic group include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, and 4-aminophenylthiophenol. Two or more of these may be used.

Preferable examples of such acid anhydrides, acid chlorides and monocarboxylic acids include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexane dicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol and 4-carboxythiophenol, and monoacylchloride compounds obtained by acid-chlorinating the carboxyl groups thereof; an active ester compound obtained by reacting a monoacyl chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2, 3-dicarboximide. Two or more of these may be used.

The alkali-soluble resin (a) used in the colored photosensitive resin composition can be synthesized by a known method. In the case of polyimide precursors, for example, polyamic acids, polyamic acid esters, and the like, as a production method, for example, the following method can be used for synthesis: a method of reacting a tetracarboxylic dianhydride with a diamine compound at a low temperature; a method of obtaining a diester by using a tetracarboxylic dianhydride and an alcohol, and then reacting the diester in the presence of an amine and a condensing agent; a method comprising obtaining a diester by using a tetracarboxylic dianhydride and an alcohol, and then acylating the residual dicarboxylic acid to react with an amine; etc.

In the case of polyimide, for example, the polyamide acid or polyamide acid ester obtained by the above method can be obtained by heating or dehydrating and ring-closing by chemical treatment with an acid, an alkali or the like.

In the case of a polybenzoxazole precursor, for example, a polyhydroxyamide, the process for producing the same can be obtained by a condensation reaction of a bisaminophenol compound and a dicarboxylic acid. Specifically, the method comprises the following steps: a method of reacting a dehydration condensing agent such as Dicyclohexylcarbodiimide (DCC) with an acid and adding a bisphenol compound thereto; dropwise adding a solution of dicarboxyl dichloride to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added; etc.

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

(B) photoacid generator

The colored photosensitive resin composition of the present invention contains (B) a photoacid generator. Examples of the photoacid generator (B) include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like, and quinone diazide compounds are preferable.

Examples of the quinone diazide compound include a compound obtained by ester-bonding a quinone diazide sulfonic acid to a polyhydroxy compound and/or a polyamino compound, a compound obtained by sulfonamide-bonding a quinone diazide sulfonic acid to a polyhydroxy compound, and a compound obtained by ester-bonding a quinone diazide sulfonic acid to a polyhydroxy polyamino compound and/or sulfonamide-bonding a sulfonamide compound. Preferably, 50mol% or more of the hydroxyl groups and amino groups of the polyhydroxy compound or polyamino compound in the quinone diazide compound are bonded to sulfonic acid of the quinone diazide relative to 100mol% of the whole. By using 50mol% or more of the substituted quinone diazide compound, the affinity of the quinone diazide compound to the aqueous alkali solution is reduced, the solubility of the resin composition in the unexposed portion in the aqueous alkali solution is greatly reduced, and the quinone diazide sulfonyl group is converted into indene carboxylic acid by exposure, so that a large dissolution rate of the resin composition in the exposed portion in the aqueous alkali solution can be obtained, and as a result, the dissolution rate ratio of the exposed portion to the unexposed portion of the composition can be increased, and a pattern can be obtained at a high resolution. By using such a quinone diazide compound, a positive photosensitive resin composition having photosensitivity to i line (365 nm), h line (405 nm) and g line (436 nm) of a usual mercury lamp can be obtained. The photoacid generator may be used alone or in combination of two or more kinds, and a photosensitive resin composition having high sensitivity can be obtained.

The quinone diazide is preferably any of a 5-sulfonyl group (5-naphthaquinone diazide) and a 4-sulfonyl group (4-naphthaquinone diazide) of naphthaquinone-5-sulfonyl group. The absorption of the diazidonaphthoquinone-5-sulfonyl ester compound extends to the g-line region of the mercury lamp, and is suitable for g-line exposure and full-wavelength exposure. The diazidonaphthoquinone-4-sulfonyl ester compound has absorption in the i-line region of the mercury lamp, and is suitable for i-line exposure. In the present invention, the diazidonaphthoquinone-4-sulfonyl ester compound or the diazidonaphthoquinone-5-sulfonyl ester compound is preferably selected according to the wavelength of the exposure to be performed. In addition, a diazidonaphthoquinone sulfonyl ester compound obtained by using a diazidonaphthoquinone-4-sulfonyl group and a diazidonaphthoquinone-5-sulfonyl group in the same molecule may be obtained, or a diazidonaphthoquinone-4-sulfonyl ester compound and a diazidonaphthoquinone-5-sulfonyl ester compound may be used in combination.

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

The content of the (B) photoacid generator is preferably 1 part by mass or more, more preferably 3 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, relative to 100 parts by mass of the (a) alkali-soluble resin. When the amount is 1 to 100 parts by mass, photosensitivity can be imparted while maintaining heat resistance, chemical resistance and mechanical properties of the cured product after heat treatment.

(C) colorant ]

The colored photosensitive resin composition of the present invention contains (C) a colorant containing (C1) a salt-forming compound containing an acid dye and a basic dye.

(C1) salt-forming Compound comprising an acid dye and a basic dye ]

The (C1) salt-forming compound containing an acid dye and a basic dye means a compound obtained by reacting an acid dye and a basic dye. The compound is obtained by chemical (salifying) reaction of an acidic dye with anionic dye ions and a basic dye with cationic dye ions, and is stable in chemical property. The colored photosensitive resin composition of the present invention contains (C1) a salt-forming compound containing an acid dye and a basic dye, instead of containing the acid dye and the basic dye separately. In comparison with the case where the acid dye and the basic dye are contained separately, the salt-forming compound is preferably contained so as not to contain the counter ion of each of the acid dye and the basic dye.

< acid dye >

The acid dye is a compound having an acidic substituent such as a sulfo group or a carboxyl group in the molecule, or an anionic water-soluble dye as a salt thereof. The acid dye includes not only the acid dye in a narrow sense but also dyes classified into direct dyes as long as the acid dye has an acid substituent such as a sulfo group or a carboxyl group.

Examples of the acid dye include c.i. acid yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; c.i. acid oranges 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; c.i. acid red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; acid brown 2, 4, 13, 248; c.i. acid violet 11, 56, 58; azo acid dyes such as c.i. acid blue 92, 102, 113, 117;

quinoline acid dyes such as c.i. acid yellow 2, 3, 5;

xanthene acid dyes such as c.i. acid red 50, 51, 52, 87, 91, 92, 93, 94, 289;

c.i. acid red 82, 92; c.i. acid violet 41, 42, 43; c.i. acid blue 14, 23, 25, 27, 40, 45, 78, 80, 127: 1. 129, 145, 167, 230; anthraquinone acid dyes such as C.I. acid green 25 and 27;

c.i. acid violet 17, 49; c.i. acid blue 7, 9, 15, 22, 83, 90; c.i. acid green 9, 50; c.i. triarylmethane acid dyes such as food green 3;

c.i. acid blue 249 and other phthalocyanine acid dyes;

indigo acid dyes such as c.i. acid blue 74;

C.i. direct yellow 4, 8, 9, 26, 44; c.i.

direct red

2, 6, 23, 28, 79, 80, 81; c.i. direct violet 1, 39; c.i. direct blue 2, 14, 15, 71, 168; c.i. direct dyes such as direct green 59; etc.

Among them, the acid dye preferably contains a xanthene acid dye and/or a triarylmethane acid dye, from the viewpoint of reducing the residue at the opening. From the viewpoint of further reducing the residue at the opening, it is more preferable to contain a xanthene acid dye such as c.i. acid red 50, 52, 289. In addition, from the viewpoint of improving the blackness (OD value) of the cured product, the xanthene acid dye further preferably contains c.i. acid red 52.

The solubility of the acid dye in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at the time of forming the sodium salt is preferably 4 mass% or more and 9 mass% or less. The salt-forming compound using an acid dye satisfying this condition can improve the film residue ratio and can further reduce the opening residue.

In the case where the acid dye is a salt other than sodium salt, the acid dye can be formed into sodium salt by using a sodium cation exchange resin or the like. The solubility in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide can be determined as follows: the sodium salt of the acid dye was added to the aqueous solution in small amounts at 25℃and dissolved by stirring, and the amount of the sodium salt added was determined from the limit at which no dissolution residue was generated.

The number of acid groups in the anionic portion of the acid dye is preferably 2 to 6 per 1000 molecular weight of the anionic portion of the acid dye. The salt-forming compound using an acid dye satisfying this condition can improve the film residue ratio and can further reduce the opening residue. The molecular weight of the anion portion can be calculated from the structural formula.

< basic dye >

The basic dye is a compound having a basic substituent such as an amino group or an imino group in a molecule, or a cationic water-soluble dye as a salt thereof.

Examples of the basic dye include c.i. basic red 17, 22, 23, 25, 29, 30, 38, 39, 46: 1. 82; basic oranges 2, 24, 25; basic violet c.i.18; c.i. basic yellow 15, 24, 25, 32, 36, 41, 73, 80; alkaline brown 1; azo basic dyes such as c.i. basic blue 41, 54, 64, 66, 67, 129;

c.i. basic red 1, 2; xanthene basic dyes such as basic violet 10 and basic violet 11;

c.i. basic yellow 11, 13, 21, 23, 28; c.i. basic orange 21; c.i. basic red 13, 14; c.i. basic violet 16, 39; an isomethine basic dye;

anthraquinone basic dyes such as c.i. basic blue 22, 35, 45, 47, etc.;

C.i.

basic violet

1, 2, 3, 4, 13, 14, 23; c.i. basic blue 1, 5, 7, 8, 11, 15, 18, 21, 24, 26; triarylmethane basic dyes such as c.i.

basic green

1 and 4.

Among them, the basic dye preferably contains a xanthene basic dye and/or a triarylmethane basic dye, and more preferably a triarylmethane basic dye, from the viewpoint of improving the blackness (OD value) of the cured product. The triarylmethane basic dye further preferably contains c.i. basic blue 7 and/or c.i. basic blue 26, from the viewpoint of further improving the blackness (OD value) of the cured product.

As described above, the acid dye preferably contains a xanthene acid dye and/or a triarylmethane acid dye. The basic dye preferably contains a xanthene basic dye and/or a triarylmethane basic dye. Preferably, both the acid dye and the basic dye contain xanthene-based basic dyes and/or triarylmethane-based basic dyes. That is, the acid dye and/or the basic dye preferably contains a xanthene dye and/or a triarylmethane dye.

The basic dye preferably has a molecular weight of 300 to 700 at the cation portion. The salt-forming compound using the basic dye satisfying this condition can improve the film residue ratio and can further reduce the opening residue. The molecular weight of the cationic moiety can be calculated from the structural formula.

(C1) The salt-forming compound containing an acid dye and a basic dye preferably contains a salt-forming compound containing one or more acid dyes and one or more basic dyes, each of which has a maximum absorption wavelength of 500nm to 700nm in a region of 350nm to 700 nm. In addition, the maximum absorption of the acid dye in the region of 350nm to 700nmWavelength is set as lambda _a The maximum absorption wavelength of the basic dye in the region of 350nm to 700nm is lambda _b In the case of lambda is preferred _a Any one of the ranges of 500nm and less than 580nm, lambda _b Any one of the ranges from 580nm to 700 nm; or lambda _a Any one of the ranges from 580nm to 700nm _b Any one of the ranges of 500nm or more and less than 580 nm. In addition, the lambda is more preferable _a And lambda is _b The absolute value of the difference is 40nm to 150 nm. The use of the salt-forming compound of an acid dye and a basic dye, which satisfy these conditions, can further improve the blackness (OD value) of the cured product.

When (C1) a salt-forming compound comprising an acid dye and a basic dye is separated into an acid dye and a basic dye and the absorption wavelength is measured, counter ions of the acid dye and the basic dye are not particularly affected, the acid dye is measured with sodium ion, and the basic dye is measured with chloride ion or bromide ion.

Salt-forming compounds of acid dyes and basic dyes can be synthesized by known methods. For example, an aqueous solution of an acid dye and an aqueous solution of a basic dye are separately formulated and mixed to produce salt-forming compounds of the acid dye and the basic dye. This is recovered by filtration, whereby the salt-forming compound can be obtained. The resulting salt-forming compound is preferably dried at about 60 to 70 ℃.

< C2) nonionic dye, (C3) pigment >

The colored photosensitive resin composition of the present invention preferably further contains (C2) a nonionic dye and/or (C3) a pigment as the colorant (C). Among them, (C2) nonionic dyes are preferably contained.

The term (C2) nonionic dye means a dye other than an acid dye and a basic dye, and does not have an ionic structure.

Examples of the nonionic dye (C2) include

C.i. disperse orange 5; c.i. disperse red 58; c.i. disperse blue 165; azo nonionic dyes such as solvent red 18;

c.i. vat blue 4; c.i. disperse red 22, 60; c.i. disperse violet 26, 28, 31; c.i. disperse blue 14, 56, 60; c.i solvent violet 13, 31, 36; and anthraquinone nonionic dyes such as c.i. solvent blue 35, 36, 45, 63, 78, 87, 97, 104, 122.

Among them, the (C2) nonionic dye is preferably an anthraquinone nonionic dye from the viewpoint of improving the blackness (OD value) of the cured product.

The (C3) pigment is a coloring compound other than a dye, and is insoluble in water and an organic solvent.

The pigment (C3) may be an organic pigment or an inorganic pigment. Examples of the organic pigment include phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, petroleum (threne) pigments, indoline pigments, benzofuranone pigments, perylene pigments, aniline pigments, azo pigments, condensed azo pigments, and carbon black. Examples of the inorganic pigment include graphite, silver-tin alloy, and fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, and oxynitrides.

In the case of using a pigment, a pigment having been subjected to surface treatment such as rosin treatment, acid group treatment, and alkali group treatment, as necessary, can be used as the pigment. In addition, a dispersant may be used together as the case may be. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.

The content of the colorant (C) in the colored photosensitive 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 component (C) is 10 parts by mass or more, light having a corresponding wavelength can be absorbed. In addition, by being 75 parts by mass or less, the opening residue can be reduced.

The content of the salt-forming compound (C1) containing an acid dye and a basic dye in the colorant (C) is preferably 10 to 90 parts by mass, more preferably 20 to 50 parts by mass. Within this range, the opening residue can be further reduced, and the film residue ratio can be further improved.

Further, the content of the (C2) nonionic dye and/or the (C3) pigment in the (C) colorant is preferably 10 to 90 parts by mass, more preferably 50 to 80 parts by mass, in total, of the content of the (C2) nonionic dye and the content of the (C3) pigment. Within this range, the opening residue can be further reduced, and the film residue ratio can be further improved.

(C4) other colorants ]

The colored photosensitive resin composition of the present invention may contain a colorant other than the (C1) salt-forming compound containing an acid dye and a basic dye, (C2) nonionic dye and/or (C3) pigment. Examples of such a colorant include dyes, organic pigments, and inorganic pigments, and may contain known colorants according to purposes.

Examples of the colorant (C) include Sumilan, lanyl (manufactured by Sumitomo chemical Co., ltd.), orasol, oracet, filamid, irgasperse, zapon, neozapon, neptune, acidol (manufactured by BASF Co., ltd.), kayaset, kayakalan (manufactured by Japanese chemical Co., ltd.), oil Colors, valifast Colors, water Colors (manufactured by Orient chemical Co., ltd.), savinyl, sandoplast, polysynthren, lanasyn (manufactured by Clariant Chemicals Co., ltd.), aizen spring (manufactured by Baotu chemical Co., ltd.), plast Color, oil Color (manufactured by Kagaku chemical Co., ltd.), and the like.

(D) thermochromic Compound

The colored photosensitive resin composition of the present invention preferably contains (D) a thermally color-developing compound. (D) The thermally color-developing compound is a compound having a maximum absorption wavelength in a region of 350nm to 700nm inclusive (hereinafter sometimes referred to as "thermally color-developing") that does not have a maximum absorption wavelength in a region of 350nm to 700nm inclusive before heating, and that has a maximum absorption wavelength in a region of 350nm to 700nm inclusive when heated at 120 ℃ to 350nm to 700nm inclusive. By using the thermally color-developing compound (D), the transmittance of 350nm to 700nm can be significantly reduced after the heat treatment. (D) The thermally color-developing compound preferably contains a compound that generates a maximum absorption wavelength in a region of 350nm to 700nm in any one of the ranges of 350nm to 500nm by heating at 120 ℃. Since (C1) the salt-forming compound containing an acid dye and a basic dye preferably has a maximum absorption wavelength of 500nm to 700nm in a region of 350nm to 700nm, the combination with (D) the thermally color-developing compound can reduce the transmittance in a wide range in the visible light region in this case.

(D) The thermally chromogenic compound is preferably one which develops thermally at a high temperature of more than 180 ℃. The higher the thermal color development temperature of the thermally color-developing compound, the more excellent the heat resistance under high temperature conditions, and the less the discoloration due to irradiation with ultraviolet light and visible light for a long period of time, the more excellent the light resistance.

(D) The thermally chromogenic compound may be a general thermosensitive dye or a pressure-sensitive dye, or may be another compound. Examples of such thermally chromogenic compounds include: a thermally chromogenic compound which changes its chemical structure and charge state by the action of an acidic group coexisting in the system upon heat treatment at 120 ℃ or higher; or a compound which causes a thermal oxidation reaction or the like at 120 ℃ or higher due to the presence of oxygen in the air, thereby thermally developing a color. Examples of the skeleton structure of the thermally color-developing compound include a triarylmethane skeleton, a diarylmethane skeleton, a fluoran skeleton, a dilactone skeleton, a phthalide skeleton, a xanthene skeleton, a rhodamine lactam skeleton, a fluorene skeleton, a phenothiazine skeleton, a phenoxazine skeleton, and a spiropyran skeleton. Specifically, there may be mentioned a compound described in Japanese patent application laid-open No. 2004-326094. Among them, a hydroxyl group-containing compound having a triarylmethane skeleton is particularly preferable because of high thermal color development temperature and excellent heat resistance. They may be used alone or in combination. In the hydroxyl group-containing compound having a triarylmethane skeleton, a naphthoquinone diazide sulfonic acid may be used as a quinone diazide compound by bonding the compound with an ester bond.

The content of the thermally color-developing compound (D) used in the present invention is preferably 5 to 80 parts by mass, particularly preferably 10 to 60 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (a). When the content of the thermally color-developing compound (D) is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet-visible light range can be reduced. Further, when the content of the thermally color-developing compound (D) 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.

The colored photosensitive resin composition of the present invention may contain various known additives such as a thermal crosslinking agent, a compound having a phenolic hydroxyl group, an adhesion improver, and a surfactant, as required, as the (a) alkali-soluble resin, (B) photoacid generator, (C) colorant, and (D) a compound other than a thermally color-developing compound.

< solvent >

The colored photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ -butyrolactone, γ -valerolactone, δ -valerolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, N' -dimethylpropylurea, N-dimethylisobutyramide, methoxy-N, N-dimethylpropionamide, ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, esters such as 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate, diacetone alcohol, alcohols such as 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. In order to dissolve the composition, the content of the solvent is preferably 100 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin (a).

< method for producing colored photosensitive resin composition >

Next, a method for producing the colored photosensitive resin composition of the present invention will be described.

The colored photosensitive resin composition of the present invention can be obtained by mixing the above-mentioned (a) alkali-soluble resin, (B) photoacid generator, (C) colorant, and if necessary, (D) thermally color-developing compound, thermal crosslinking agent, compound having phenolic hydroxyl group, adhesion improver, surfactant, solvent, etc. as components constituting the colored photosensitive resin composition. The colored photosensitive resin composition to be used in the method for producing a colored photosensitive resin composition film of the present invention described later preferably contains a solvent and dissolves the above components. In this case, as a method for promoting dissolution, heating and stirring are mentioned. In the case of heating, the heating temperature is preferably set within a range that does not impair the performance of the colored photosensitive resin composition, and is usually from room temperature to 80 ℃. In the present specification, room temperature means 25 ℃. The order of dissolving the components is not particularly limited, and examples thereof include a method of sequentially dissolving compounds having low solubility in a solvent. In the case of stirring, the rotation speed is preferably set within a range not impairing the performance of the colored photosensitive resin composition, and is usually 200rpm to 2000rpm. In the case of stirring, heating may be carried out as required, and is usually at room temperature to 80 ℃. In addition, as for the components such as the surfactant and a part of the adhesion improver which are liable to generate bubbles during stirring and dissolution, by adding the components after dissolving the other components at the end, it is possible to prevent the other components from being poorly dissolved due to the generation of bubbles.

The obtained colored photosensitive resin composition is preferably filtered using a filter to remove dust and particles. The pore diameter of the filter is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but is not limited thereto. The material of the filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., but polyethylene and nylon are preferable. In the case where the organic pigment is contained in the colored photosensitive resin composition, a filter having a pore diameter larger than the particle diameter thereof is preferably used.

The colored photosensitive resin composition of the present invention is preferably used for a pixel dividing layer of an organic EL display device.

< cured product obtained by curing colored photosensitive resin composition >

A cured product obtained by curing the colored photosensitive resin composition of the present invention will be described.

The cured product obtained by curing the colored photosensitive resin composition is a cured product obtained by applying the colored photosensitive resin composition to a substrate or the like and performing a heat treatment to cure the composition. The heat treatment conditions are preferably 200℃or higher, more preferably 250℃or higher. The heat treatment condition is preferably 400 ℃ or lower, more preferably 350 ℃ or lower.

In the cured product obtained by curing the colored photosensitive resin composition of the present invention, the film thickness is preferably 1.0 μm to 5.0 μm, more preferably 3.5 μm to 5.0 μm, in view of further improving the blackness (OD value) of the cured product. The colored photosensitive resin composition of the present invention has sufficient alkali solubility, and even if a thick film is formed, the residue is less, and the pattern can be sufficiently opened.

The OD value of the cured product per 1 μm film thickness is preferably 0.5 to 2.0. For example, the content of the (C) colorant is set to 12 to 75 parts by mass relative to 100 parts by mass of the (a) alkali-soluble resin, and the content of the (C1) salt-forming compound containing the acid dye and the basic dye in the (C) colorant is set to 25 to 100 parts by mass, whereby the cured product can be set to a desired OD value.

Further, in the CIE Lab color space display system, it is preferable that the reflectance chromaticity of the cured product has an a value of-30 or more and 30 or less and a b value of-30 or more and 30 or less. For example, by using a salt-forming compound containing an acid dye and a basic dye, which has a difference in maximum absorption wavelength between the acid dye and the basic dye in a region of 350nm to 700nm inclusive, in (C1), the cured product can have a desired reflectance. By setting the values of a and b in this range, a cured product that is more black can be obtained, and a display device including the cured product can be a higher-quality display device.

< method for producing cured product Using colored photosensitive resin composition >

A method for producing a cured product using the colored photosensitive resin composition of the present invention will be described.

The method for producing a cured product comprises the steps of: (1) A step of forming a coating film by applying the colored photosensitive resin composition to a substrate; (2) Exposing the coating film with active chemical rays to obtain an exposed coating film; (3) Developing the exposed coating film with an alkali solution to obtain a developed coating film; and (4) heating the developed coating film to obtain a cured product.

(1) In the step of forming a coating film of the colored photosensitive resin composition, the colored photosensitive resin composition of the present invention is coated by spin coating, slit coating, dip coating, spray coating, printing, or the like, to obtain a coating film of the colored photosensitive resin composition. The substrate to be coated with the colored photosensitive resin composition may be pretreated with the above-mentioned adhesion improver in advance before coating. For example, the surface of the substrate is treated with a solution obtained by dissolving the adhesion improver in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, or the like in an amount of 0.5 to 20 mass%. Examples of the method for treating the surface of the substrate include spin coating, slot die coating, bar coating, dip coating, spray coating, and vapor treatment. In the step of drying the coating film, the coating film obtained by the film formation is subjected to a reduced pressure drying treatment as needed, and then subjected to a heat treatment at 50 to 180 ℃ for 1 minute to several hours using a heating plate, an oven, infrared rays, or the like, thereby obtaining the coating film.

Next, a step (2) of exposing the coating film with active chemical rays to obtain an exposed coating film will be described.

The coating film is irradiated with active chemical rays (hereinafter, may be referred to as exposure). In this case, the exposure may be performed through a photomask having a desired pattern, or the coating film may be directly exposed with a laser or the like, as necessary. The active chemical rays used for exposure include ultraviolet rays, visible rays, electron rays, X-rays, etc., but in the present invention, i-rays (365 nm), h-rays (405 nm), g-rays (436 nm) of mercury lamps are preferably used.

Next, a step (3) of developing the exposed coating film with an alkali solution to obtain a developed coating film will be described.

The exposed coating film is developed with an alkali solution to remove the exposed portion of the coating film. The developer in this case is preferably an aqueous solution of a compound exhibiting basicity 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, and 1, 6-hexamethylenediamine. In addition, one or more kinds of polar solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, γ -butyrolactone, dimethylacrylamide, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added to these alkaline aqueous solutions. The development method may be a method such as spraying, spin-coating immersion, dipping, or ultrasonic.

Next, the pattern formed by the development is preferably rinsed with distilled water. Here, alcohols such as ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and the like may be added to distilled water to carry out the washing treatment.

Next, a step (4) of heat-treating the developed coating film to obtain a cured product will be described.

The heat treatment of the developed coating film can remove components having low heat resistance and residual solvents, and thus can improve the heat resistance and chemical resistance of the cured product. The heating treatment is performed for 5 minutes to 5 hours while a temperature is selected to be raised stepwise or a temperature is selected to be raised continuously in a certain temperature range. For example, a method of heat treatment at 230℃for 60 minutes may be mentioned. In the present invention, the heating treatment conditions are preferably 200℃or higher, more preferably 230℃or higher. The heat treatment condition is preferably 400℃or lower, more preferably 350℃or lower.

< display device >

The display device of the present invention comprises a cured product obtained by curing the colored photosensitive resin composition.

The cured product obtained by curing the colored photosensitive resin composition is included in a planarization layer and a pixel division layer of a display device having a substrate on which a TFT is formed, a planarization layer on a driving circuit, a pixel division layer and a display element on a first electrode, and a second electrode in this order. Examples of the display device having such a structure include a liquid crystal display device and an organic EL display device. Among them, the organic EL display device is suitable for use in an organic EL display device requiring high heat resistance and low outgas (outgas) properties for a planarization layer and a pixel-dividing layer, and is particularly suitable for use in a pixel-dividing layer.

The cured product obtained by curing the colored photosensitive resin composition of the present invention may be used for either the planarization layer or the pixel dividing layer, or both. An active matrix display device includes a TFT and a wiring which is located on a side of the TFT and connected to the TFT on a substrate such as glass, and a planarizing layer which covers the TFT. The display element and the wiring are connected through a contact hole formed in the planarization layer.

Examples

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

(1) Evaluation of film residue Rate

The colored photosensitive resin compositions (hereinafter, sometimes referred to as "resin liquid") prepared in examples and comparative examples were spin-coated on a glass substrate (manufactured by GEOMATEC Co., ltd.; hereinafter, referred to as "ITO substrate") having ITO formed thereon by sputtering, and pre-baked at 120℃for 120 seconds using a warning heating plate (HPD-3000 BZN; manufactured by As One Co., ltd.) so that the film thickness after pre-baking became 3.0. Mu.m. To obtain a desired film thickness, the obtained pre-baked film was developed with 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, followed by rinsing with pure water to obtain a developed film.

The film thicknesses of the pre-baked film and the developed film were measured by using a stylus profiler (P-15; manufactured by KLA-Tencor Co., ltd.), and the residual film ratio was determined from the values thereof by using the following formula.

Residual film ratio [% ] = (film thickness of developed film)/(film thickness of pre-baked film) ×100.

(2) Evaluation of opening residue

The evaluation of the opening residues was performed by evaluating the light-emitting area ratio of an organic EL display device having a cured product formed from the colored photosensitive resin compositions prepared in examples and comparative examples as a pixel-divided layer.

Fig. 1 (a) to (d) show schematic diagrams of the substrate used. First, an ITO transparent conductive film of 10nm was formed on the entire surface of an alkali-free glass substrate 1 of 38X 46mm by sputtering, and etched as a first electrode 2. In addition, the auxiliary electrode 3 is also formed simultaneously for removing the second electrode (fig. 1 (a)). The obtained substrate was subjected to ultrasonic washing with "semiconductor lean" (registered trademark) 56 (trade name, manufactured by Furuuchi chemical co., ltd.) for 10 minutes, and then washed with ultrapure water. Next, the photosensitive resin compositions prepared in each example and comparative example were applied to the entire surface of the substrate by spin coating, and baked on a heating plate at 100 ℃ for 2 minutes. After UV exposure of the film via a photomask, development was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, and after only the exposed portion was dissolved, the film was rinsed with pure water. The resulting pattern was cured in an oven at 230 ℃ for 60 minutes under a nitrogen atmosphere. In this way, openings having a width of 70 μm and a length of 260 μm are arranged at a pitch of 155 μm in the width direction and at a pitch of 465 μm in the length direction, and the pixel-divided layer 4 is formed so as to be limited to the substrate effective region, and the pixel-divided layer 4 has a shape in which the first electrode is exposed at each opening (fig. 1 (b)). The opening portion is finally a light-emitting pixel. The effective area of the substrate was 16mm square, and the thickness of the insulating layer was about 1.0. Mu.m.

Next, the substrate on which the first electrode 2, the auxiliary electrode 3, and the pixel dividing layer 4 are formed is used to manufacture an organic EL display device. After nitrogen plasma treatment as the pretreatment, the organic EL layer 5 including the light-emitting layer was formed by a vacuum evaporation method (fig. 1 (c)). The vacuum degree at the time of vapor deposition was 1×10 ^-3 Pa or less, the substrate is rotated relative to the vapor deposition source during vapor deposition. First, 10nm of compound (HT-1) was deposited as a hole injection layer, and 50nm 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 at a thickness of 40nm so that the doping concentration became 10%. Then, the compounds (ET-1) and (LiQ) as electron transport materials were mixed in an amount of 1:1 are laminated to a thickness of 40 nm. The structure of the compound used in the organic EL layer is as follows.

[ chemical formula 8]

Next, a 2nm compound (LiQ) was evaporated, followed by 10: the second electrode 6 was produced by vapor deposition of MgAg at a volume ratio of 1 to 10nm (fig. 1 (d)). Finally, the cover glass plate was bonded with an epoxy resin adhesive under a low humidity nitrogen atmosphere to seal, and 4 light emitting devices having a square of 5mm were fabricated on 1 substrate. Here, the film thickness refers to a display value of a crystal oscillation type film thickness monitor.

At 10mA/cm ² The organic EL display device manufactured by the above method was caused to emit light by dc driving, and the area of the light-emitting region was measured, and the light-emitting area ratio was obtained by the following formula. From this value, the opening residue was judged as follows.

Area ratio of light emission [% ] = area of area where light is emitted/area of light emitting pixel x 100

S: the light-emitting area ratio is 95% to 100%

A: the light-emitting area ratio is more than 90% and less than 95%

B: the light-emitting area ratio is more than 75% and less than 90%

C: the light emitting area ratio is less than 75%.

(3) Evaluation of blackness (OD value)

The resin solution was spin-coated on a 5-inch square glass substrate so that the film thickness after the heat treatment (curing) became 1.5. Mu.m, and was prebaked at 120℃for 120 seconds to prepare a prebaked film. Then, a heat-resistant colored resin film (cured product) was produced by curing at 230℃for 60 minutes in an atmosphere using a high-temperature clean oven INH-9CD-S manufactured by KOYO THERMO SYSTEM Co. The film thickness of the heat-resistant colored resin film (cured product) was measured using a stylus profiler. The OD value of the heat-resistant colored resin film (cured product) thus obtained was measured by using an optical concentration meter (361 TVreal; manufactured by X-Rite Co.).

When the film thickness of the cured film was not 1.5 μm, the light transmittance was converted to 1.5 μm.

(4) Evaluation of reflectance chromaticity

In the evaluation of the blackness (OD value) of (3), a heat-resistant colored resin film (cured product) was produced in the same manner as the above-described evaluation, except that a 5-inch square glass substrate (manufactured by geomotec corporation) having ITO/Ag (10 nm/100 nm) formed thereon was used as a substrate instead of the 5-inch square glass substrate, and reflection chromaticities a and b of specular reflection light (SCI system) were measured using a spectrocolorimeter (manufactured by CM-2600d;Konica Minolta).

Synthesis example 1

Into a three-necked flask, 18.31g (0.05 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by CENTRAL GLASS Co., ltd., hereinafter referred to as BAHF), 17.4g (0.3 mol) of propylene oxide (manufactured by Tokyo chemical Co., ltd.), and 100ml of acetone were weighed and dissolved. A solution of 20.41g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 10mL of acetone was added dropwise thereto. After the completion of the dropwise addition, it was reacted at-15℃for 4 hours, and then returned to room temperature. The white solid precipitated was filtered off and dried in vacuo at 50 ℃. 30g of the obtained solid was placed in a 300mL stainless steel autoclave, dispersed in 250mL 2-methoxyethanol, and 2g of 5% palladium-carbon (Fuji photo-Kagaku Co., ltd.) was added. Hydrogen was introduced thereinto by using a balloon, and the mixture was allowed to react at room temperature for 2 hours. After 2 hours, it was confirmed that the balloon did not shrink any further. After the completion of the reaction, the palladium compound as a catalyst was removed by filtration, and the resultant was concentrated by distillation under reduced pressure to obtain a hydroxyl group-containing diamine compound (HA) having the following structure.

[ chemical formula 9]

15.1g (0.025 mol) of HA, 3.66g (0.01 mol) of BAHF and 0.62g (0.0025 mol) of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (hereinafter referred to as SiDA) were dissolved in 200g of N-methylpyrrolidone (NMP) under a stream of dry nitrogen. 22.2g (0.05 mol) of 2,2- (3, 4-dicarboxyphenyl) hexafluoropropane (hereinafter referred to as 6 FDA) and 50g of NMP were added thereto, and stirred at 40℃for 1 hour. Then, 2.73g (0.025 mol) of 3-aminophenol (hereinafter referred to as MAP, manufactured by Tokyo chemical Co., ltd.) was added thereto, and the mixture was stirred at 40℃for 1 hour. Further, a solution obtained by diluting 11.9g (0.1 mol) of N, N-dimethylformamide dimethyl acetal (manufactured by Mitsubishi Yang Zhushi Co., ltd., hereinafter referred to as DFA) with 5g of NMP was charged, and stirring was continued at 40℃for 2 hours. After the stirring was completed, the solution was poured into 2L of water, and the precipitate of polymer solid was collected by filtration. Further, the polymer solid was dried with a vacuum drier at 50℃for 72 hours by washing with 2L of water 3 times to obtain a polyimide precursor resin a-1 as the alkali-soluble resin (A).

Synthesis example 2

42.4g (0.1 mol) of 4,4' - [1- [4- [1- (4-hydroxyphenyl-1) -1-methylethyl ] phenyl ] ethylene ] bisphenol (TrisP-PA, manufactured by Nitsa chemical industry Co., ltd.) and 72.3g (0.27 mol) of naphthoquinone diazide-5-sulfonyl chloride (manufactured by Toyo Seisaku-de Co., ltd.) were dissolved in 450g of 1, 4-dioxane under a dry nitrogen stream, and the mixture was adjusted to room temperature. 25.0g of triethylamine mixed with 100g of 1, 4-dioxane was added dropwise thereto so that the temperature in the system did not reach 35℃or higher. After the dropwise addition, the mixture was stirred at 40℃for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitate was collected by filtration and washed with 1L of 1% aqueous hydrochloric acid. Then, the mixture was washed with 2L of water 2 times. The precipitate was dried in a vacuum dryer to obtain a quinone diazide compound b-1 represented by the following formula.

Synthesis example 3

Into a separable flask, 9.25g (0.018 mol) of c.i. basic blue 7 (manufactured by tokyo chemical industry Co., ltd.) as a basic dye and 200g of pure water were charged, and stirred at 60℃for 30 minutes. An aqueous solution obtained by dissolving 11.50g (0.019.8 mol) of c.i. acid red 52 (manufactured by fuji film and photoplethysmography) as an acid dye in 120g of pure water was charged, followed by stirring at 60 ℃ for 60 minutes. Then, after cooling to room temperature, the reaction solution was filtered to obtain a purple solid. The solid was dried at 60℃for 8 hours to give a salt-forming compound c1-1.

Synthesis examples 4 to 10

Salt-forming compounds c1-2 to c1-8 were obtained by the same method as in Synthesis example 3, using the compounds shown in Table 1 as basic dye and acid dye.

TABLE 1

The compounds shown in each example and comparative example are as follows.

(C2) Nonionic dye

c2-1: c.i. solvent blue 45

c2-2: c.i. solvent blue 63

c2-3: c.i. solvent Red 18

c2-4: c.i. disperse Violet 31

(C3) Pigment

c3-1: c.i. pigment blue 60

(C4) Other colorants

c4-1: c.i. acid red 52.

(B) The structures of the photoacid generator b-1, (D) the thermally chromogenic compound D-1, the thermal crosslinking agent e-1 as another additive, the compound f-1 having a phenolic hydroxyl group, and the adhesion improver g-1 are shown below.

[ chemical formula 10]

Example 1

The polyimide precursor resin a-1 obtained in synthesis example 1 as (a) an alkali-soluble resin, the compound B-1 obtained in synthesis example 2 as (B) a photoacid generator, the compound C1-1 obtained in synthesis example 3 as (C1) a salt-forming compound containing an acid dye and a basic dye, the compound C2-1 as (C2) a nonionic dye, the compound D-1 as (D) a thermally color-developing compound, the thermal crosslinking agent e-1 as other additives, the compound f-1 having a phenolic hydroxyl group, the adhesion improver g-1, and the compound C1 as a solvent were added in the amounts shown in table 1 under a yellow lamp in a mass ratio of 1:1 gamma-lactone (GBL) and Ethyl Lactate (EL), and stirring to dissolve the same, to prepare a composition 1.

Regarding composition 1, evaluation of film residue, opening residue, OD value, and reflectance was performed.

Examples 2 to 16 and comparative examples 1 to 3

Compositions 2 to 19 were prepared in the same manner as in example 1, with the compositions shown in Table 2.

Compositions 2 to 19 were evaluated in the same manner as in example 1. The evaluation results are shown in table 3.

Example 17

50g of the polyimide resin a-1 obtained in Synthesis example 1 as an alkali-soluble resin (A), 100g of the compound C3-1 as a pigment (C3) and 1000g of gamma-butyrolactone were charged in a pot, and stirred with a homomixer for 20 minutes to obtain a pre-dispersion. To be filled with 75 volume percent

Centrifugal separation of zirconia beadsHiroshima Metal of separator&The obtained pre-dispersion was supplied to an Ultra Apex Mill of a disperser manufactured by Machinery Co., ltd.) and dispersed at a rotational speed of 10m/s for 3 hours to obtain a pigment dispersion.

4.5g of the pigment dispersion was mixed with 3.28g of the polyimide resin a-1 obtained in Synthesis example 1 as an alkali-soluble resin (A), 1.0g of the compound B-1 obtained in Synthesis example 2 as a photoacid generator (B), 0.35g of the compound C1-1 obtained in Synthesis example 3 as a salt-forming compound containing an acid dye and a basic dye (C1), 0.7g of the compound D-1 as a thermally color-developing compound (D), 0.6g of the thermal crosslinking agent e-1 as another additive, 0.4g of the compound f-1 having a phenolic hydroxyl group, 0.1g of the sealing agent g-1, 5.5g of gamma-butyrolactone (GBL) as a solvent, and 10g of Ethyl Lactate (EL), and stirred to dissolve them, to prepare a composition 20.

Composition 20 was evaluated in the same manner as in example 1. The evaluation results are shown in table 3.

Example 18

In example 2, composition 2 was evaluated by the same method except that (2) evaluation of the opening residue was performed so that the thickness of the insulating layer became 3.5 μm, and (3) evaluation of the blackness (OD value) and (4) evaluation of the reflectance were performed so that the thickness of the heat-resistant colored resin film (cured product) became 3.5 μm. The evaluation results are shown in table 3.

TABLE 2

[ Table 2]

TABLE 3

[ Table 3]

From the above results, it was confirmed that the colored photosensitive resin composition of the present invention can form a pattern while satisfying the characteristics of the residual film ratio, the opening residue, and the blackness.

Description of the reference numerals

1: glass substrate

2: first electrode

3: auxiliary electrode

4: pixel dividing layer

5: organic EL layer

6: second electrode

Claims

1. A colored photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the (C) colorant comprises (C1) a salt-forming compound comprising an acid dye and a basic dye.

2. The colored photosensitive resin composition according to claim 1, wherein the (C1) salt-forming compound comprising an acid dye and a basic dye contains a salt-forming compound comprising one or more acid dyes and one or more basic dyes, and the maximum absorption wavelength of the one or more acid dyes and the one or more basic dyes in a region of 350nm to 700nm inclusive is 500nm to 700nm inclusive.

3. The colored photosensitive resin composition according to claim 1 or 2, wherein the colored photosensitive resin composition is used for a pixel dividing layer of an organic EL display device.

4. The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the acid dye has a solubility in a 2.38 mass% tetramethylammonium hydroxide aqueous solution of 4 mass% to 9 mass% when formed into a sodium salt.

5. The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the number of acid groups in the anionic portion of the acid dye is 2 to 6 per 1000 molecular weight of the anionic portion of the acid dye.

6. The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the molecular weight of the cationic part in the basic dye is 300 to 700.

7. The colored photosensitive resin composition according to any one of claims 1 to 6, wherein a maximum absorption wavelength of the acid dye in a region of 350nm to 700nm inclusive is represented by λ _a Setting the maximum absorption wavelength of the basic dye in the region of 350nm to 700nm at lambda _b Lambda is at the time _a Any one of the ranges of 500nm and less than 580nm, lambda _b Any one of the ranges from 580nm to 700 nm; or lambda _a Any one of the ranges from 580nm to 700nm _b Any one of the ranges of 500nm or more and less than 580 nm.

8. The colored photosensitive resin composition according to claim 7, wherein the λ _a With said lambda _b The absolute value of the difference is 40nm to 150 nm.

9. The colored photosensitive resin composition according to any one of claims 1 to 8, further comprising (D) a thermally color-developing compound.

10. The colored photosensitive resin composition according to claim 9, wherein the (D) thermally color-developing compound comprises: by heating at 120 ℃ or higher, a compound having a maximum absorption wavelength is generated in a region of 350nm or more and 700nm or less in any one of the ranges of 350nm or more and 500nm or less.

11. The colored photosensitive resin composition according to any one of claims 1 to 10, wherein the (a) alkali-soluble resin contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor and copolymers thereof.

12. The colored photosensitive resin composition according to any one of claims 1 to 11, wherein the acid dye and/or the basic dye contains a xanthene dye and/or a triarylmethane dye.

13. The colored photosensitive resin composition according to any one of claims 1 to 12, further comprising (C2) a nonionic dye and/or (C3) a pigment.

14. The colored photosensitive resin composition according to claim 13, which contains the (C2) nonionic dye, the (C2) nonionic dye containing an anthraquinone-based nonionic dye.

15. The colored photosensitive resin composition according to any one of claims 1 to 14, wherein the content ratio of the (C) colorant is 10 to 75 parts by mass relative to 100 parts by mass of the (a) alkali-soluble resin.

16. A cured product obtained by curing the colored photosensitive resin composition according to any one of claims 1 to 15.

17. The cured product according to claim 16, wherein the cured product has a film thickness of 1.0 μm or more and 5.0 μm or less.

18. The cured product according to claim 16 or 17, wherein the cured product has a film thickness of 3.5 μm or more and 5.0 μm or less.

19. The cured product according to any one of claims 16 to 18, wherein the OD value of the cured product per 1 μm film thickness is 0.5 to 2.0.

20. The cured product according to any one of claims 16 to 19, wherein in a CIE Lab color space display system, a value of a reflection chromaticity of the cured product is-30 or more and 30 or less, and b value is-30 or more and 30 or less.

21. A display device comprising the cured product according to any one of claims 16 to 20.

22. A method for producing a cured product, which comprises, in order:

(1) A step of forming a coating film by applying the colored photosensitive resin composition according to any one of claims 1 to 15 to a substrate;

(2) Exposing the coating film with active chemical rays to obtain an exposed coating film;

(3) Developing the exposed coating film with an alkali solution to obtain a developed coating film; and

(4) And heating the developed coating film to obtain a cured product.