Positive photosensitive resin composition and organic EL element partition wall

Abstract

To provide a chemical amplification photosensitive resin composition which contains a metal complex dye, and has high sensitivity.SOLUTION: A method for producing a positive type photosensitive resin composition that contains a first resin (A) having a plurality of alkali-soluble functional groups, in which at least a part of the plurality of alkali-soluble functional groups is protected with an acid decomposable group, an optical acid generator (B), and a metal complex dye (C) containing an ammonium cation includes the following step 1 and step 2. Step 1: modification step of reacting a metal complex dye precursor (c) containing an ammonium cation with a compound having an amine reactive functional group, and thereby reducing an ammonium cation content in the metal complex dye precursor (c), and obtaining a metal complex dye (C). Step 2: mixing step of mixing a first resin (A), an optical acid generator (B), and the metal complex dye (C) obtained in the step 1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a positive-type photosensitive resin composition, an organic EL device partition wall, an organic EL device insulating film, and an organic EL device each using the same. More specifically, the present invention relates to a positive-type photosensitive resin composition containing a metal complex dye, and an organic EL device partition wall, an organic EL device insulating film, and an organic EL device each using the same. [Background technology]

[0002] In display devices such as organic light-emitting diode (OLED) displays, partition walls are used in the gaps between colored patterns in the display area or around the edges of the display area to improve display characteristics. In the manufacture of organic EL display devices, partition walls are first formed to prevent organic material pixels from contacting each other, and then organic material pixels are formed between the partition walls.

[0003] These partition walls are generally formed by photolithography using a photosensitive resin composition and have insulating properties. Specifically, a photosensitive resin composition is applied to a substrate using a coating device, and volatile components are removed by heating or other means. The resulting pattern is then developed by removing the unexposed portions (in the case of a negative-tone pattern) or the exposed portions (in the case of a positive-tone pattern) with a developer such as an alkaline aqueous solution. The resulting pattern is then heat-treated to form partition walls (insulating films). Next, organic materials that emit light in three colors (red, green, and blue) are deposited between the partition walls by inkjet printing or other methods to form the pixels of the organic EL display device.

[0004] In recent years, in this field, due to the miniaturization of display devices and the diversification of displayed content, there has been a demand for higher pixel performance and higher resolution. Attempts have been made to impart light-blocking properties to partition wall materials using colorants in order to increase the contrast and improve visibility in display devices. However, when partition wall materials are imparted with light-blocking properties, the photosensitive resin composition tends to have low sensitivity, which may result in longer exposure times and reduced productivity. Therefore, photosensitive resin compositions used to form partition wall materials containing colorants are required to have higher sensitivity.

[0005] Patent Document 1 (JP 2001-281440 A) describes a radiation-sensitive resin composition that exhibits high light-blocking properties through heat treatment after exposure, in which titanium black is added to a positive-tone radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound.

[0006] Patent Document 2 (JP 2002-116536 A) describes a method for blackening a partition wall material by using carbon black in a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] a 1,2-quinonediazide compound, and [C] a colorant.

[0007] Patent Document 3 (JP 2010-237310 A) describes a radiation-sensitive resin composition that exhibits light-blocking properties by heat treatment after exposure, in which a heat-sensitive dye is added to a positive-tone radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound.

[0008] Patent Document 4 (WO 2017 / 069172) describes a positive photosensitive resin composition containing (A) a binder resin, (B) a quinone diazide compound, and (C) at least one black dye selected from black dyes defined by the color index of Solvent Black 27 to 47. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-281440 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-116536 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-237310 [Patent Document 4] International Publication No. 2017 / 069172 Summary of the Invention [Problem to be solved by the invention]

[0010] In the photosensitive resin composition used to form a colored partition wall material, a considerable amount of colorant must be used to sufficiently enhance the light-shielding properties of the cured film. When such a large amount of colorant is used, the radiation irradiated onto the coating of the photosensitive resin composition is absorbed by the colorant, reducing the effective intensity of the radiation in the coating and resulting in insufficient exposure of the photosensitive resin composition, resulting in poor pattern formability.

[0011] In forming the partition wall in the organic EL element, it is important from the viewpoint of productivity and the like that the material for forming the partition wall has high sensitivity.

[0012] A widely known method for increasing the sensitivity of photosensitive resin compositions is to use chemically amplified photosensitive resin compositions. Chemically amplified photosensitive resin compositions generally contain a resin in which alkali-soluble functional groups are protected with acid-decomposable groups, and a photoacid generator. The acid generated from the photoacid generator upon exposure promotes the decomposition (deprotection) of the acid-decomposable groups, regenerating the alkali-soluble functional groups. This promotes alkaline dissolution of the resin in the exposed areas during development. The acid derived from the photoacid generator decomposes one acid-decomposable group, then regenerates it, and contributes to the decomposition of another acid-decomposable group. The apparent quantum efficiency of a chemically amplified system based on the above reaction mechanism is expressed as the product of the quantum efficiency of acid generation and the reaction chain. Therefore, high sensitivity can be achieved by using a chemically amplified photosensitive resin composition.

[0013] However, the present inventors have found that when a metal complex dye is used as a colorant in a chemically amplified photosensitive resin composition, if the dye is dissolved in an organic solvent without any further processing and then immediately used in formulation, the sensitivity of the photosensitive resin composition decreases.

[0014] An object of the present invention is to provide a highly sensitive chemically amplified photosensitive resin composition containing a metal complex dye. [Means for solving the problem]

[0015] The present inventors have found that the sensitivity of a chemically amplified photosensitive resin composition can be increased by reacting the ammonium cations constituting the metal complex dye with a compound having an amine-reactive functional group by means of heating, storing at room temperature, or the like, and thereby reducing the content of the ammonium cations from the initial state.

[0016] That is, the present invention includes the following aspects. [1] A method for producing a positive photosensitive resin composition comprising: a first resin (A) having a plurality of alkali-soluble functional groups, at least some of which are protected with acid-decomposable groups; a photoacid generator (B); and a metal complex dye (C) containing an ammonium cation, the method comprising the following steps 1 and 2: Step 1: A modification step in which a metal complex dye precursor (c) containing an ammonium cation is reacted with a compound having an amine-reactive functional group to reduce the ammonium cation content in the metal complex dye precursor (c) to obtain a metal complex dye (C). Step 2: A mixing step of mixing the first resin (A), the photoacid generator (B), and the metal complex dye (C) obtained in step 1. [2] The method for producing a positive photosensitive resin composition according to [1], wherein the compound having an amine-reactive functional group is at least one selected from the group consisting of ketones and esters. [3] The method for producing a positive photosensitive resin composition according to [1] or [2], wherein the compound having an amine-reactive functional group is γ-butyrolactone. [4]

[0023] The method for producing a positive photosensitive resin composition according to any one of [1] to [3], wherein in step 1, the metal complex dye precursor (c) is reacted with the compound having an amine-reactive functional group so that the content of ammonium cations in the metal complex dye (C) is 21 mass% or less. [5] [4] The method for producing a positive photosensitive resin composition according to any one of [1] to [4], wherein in the step 1, the compound having an amine-reactive functional group is used as a solvent, the metal complex dye precursor (c) is dissolved in the solvent, and the resulting solution is stirred or allowed to stand. [6] The method for producing a positive photosensitive resin composition according to any one of [1] to [5], wherein in the step 1, the reaction temperature is 0 to 200°C. [7] The method for producing a positive photosensitive resin composition according to any one of [1] to [6], wherein in step 1, the reaction time is 0.01 hours or more. [8] The method for producing a positive photosensitive resin composition according to any one of [1] to [7], wherein the metal element forming the metal complex ion contained in the metal complex dye precursor (c) is at least one selected from the group consisting of chromium, copper, cobalt, nickel, and iron. [9] The method for producing a positive photosensitive resin composition according to any one of [1] to [8], wherein the metal complex dye precursor (c) is at least one black dye defined by the color index (CI) of Solvent Black 22 to 47.

[10] The method for producing a positive photosensitive resin composition according to any one of [1] to [9], wherein the first resin (A) is a resin having a plurality of phenolic hydroxyl groups, at least a part of the plurality of phenolic hydroxyl groups being protected with the acid-decomposable group.

[11]

[10] The method for producing a positive photosensitive resin composition according to

[10] , wherein the first resin (A) is a copolymer of a polymerizable monomer having one or more phenolic hydroxyl groups, at least a part or all of which are protected with the acid-decomposable group, and another polymerizable monomer.

[12] The first resin (A) is represented by the formula (3): [ka] (In formula (3), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R5 is the acid-decomposable group, r is an integer of 0 to 5, and s is an integer of 0 to 5, with the proviso that r+s is an integer of 1 to 5. and at least one structural unit represented by formula (3) in which s is an integer of 1 or more.

[13] The first resin (A) is represented by the formula (2): [ka] (In formula (2), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The method for producing a positive photosensitive resin composition according to either

[11] or

[12] , which has a structural unit represented by the following formula:

[14] The method for producing a positive photosensitive resin composition according to any one of [1] to

[13] , wherein the positive photosensitive resin composition further comprises a second resin (D), and the second resin (D) is at least one selected from the group consisting of a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group, and a resin having an epoxy group and a phenolic hydroxyl group, and does not have the alkali-soluble functional group protected by the acid-decomposable group.

[15] The method for producing a positive photosensitive resin composition according to any one of [1] to

[14] , wherein the positive photosensitive resin composition contains the metal complex dye (C) in an amount of 10% by mass to 60% by mass based on 100% by mass of the solid content.

[16] The method for producing a positive photosensitive resin composition according to any one of [1] to

[15] , wherein the positive photosensitive resin composition contains the photoacid generator (B) in an amount of 1% by mass to 50% by mass based on 100% by mass of the solid content.

[17] The method for producing a positive photosensitive resin composition according to any one of [1] to

[16] , wherein the optical density (OD value) of a cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness.

[18] A positive photosensitive resin composition comprising: a first resin (A) having a plurality of alkali-soluble functional groups, at least a portion of which are protected with acid-decomposable groups; a photoacid generator (B); and a metal complex dye (C) containing ammonium cations, wherein the ammonium cation content in the metal complex dye (C) is 21 mass% or less.

[19] A partition wall for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to

[18] .

[20] An insulating film for an organic electroluminescence device, comprising a cured product of the positive photosensitive resin composition according to

[18] . [twenty one] An organic electroluminescence device comprising a cured product of the positive photosensitive resin composition according to

[18] . [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a highly sensitive chemically amplified photosensitive resin composition containing a metal complex dye. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below.

[0019] In this disclosure, "alkali-soluble" and "alkali aqueous solution soluble" mean that the positive photosensitive resin composition or its components, or a coating or cured coating of the positive photosensitive resin composition, is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. The term "alkali-soluble functional group" refers to a group that imparts such alkali-solubility to the positive photosensitive resin composition or its components, or a coating or cured coating of the positive photosensitive resin composition. Examples of alkali-soluble functional groups include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group.

[0020] In the present disclosure, the term "acid-decomposable group" refers to a group that is decomposed (deprotected) in the presence of an acid, optionally with heating, to generate an alkali-soluble functional group.

[0021] In the present disclosure, the term "radically polymerizable functional group" refers to an ethylenically unsaturated group, and the term "radically polymerizable compound" refers to a compound having one or more ethylenically unsaturated groups.

[0022] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0023] In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin, polymer, or copolymer refer to values ​​calculated as standard polystyrene, measured by gel permeation chromatography (GPC).

[0024] In the present disclosure, the term "resin component" refers to the total component of the first resin (A) and the second resin (D).

[0025] In the present disclosure, the term "solid content" refers to the total mass of components in a positive photosensitive resin composition, including the first resin (A), the photoacid generator (B), the metal complex dye (C), the second resin (D), the dissolution promoter (E), and the optional component (F), but excluding the solvent (G).

[0026] [Method for producing a positive-type photosensitive resin composition] A method for producing a positive photosensitive resin composition according to one embodiment relates to a positive photosensitive resin composition including a first resin (A) having a plurality of alkali-soluble functional groups, at least some of which are protected with acid-decomposable groups, a photoacid generator (B), and a metal complex dye (C) containing an ammonium cation, and includes the following steps 1 and 2: Step 1: A modification step in which a metal complex dye precursor (c) containing an ammonium cation is reacted with a compound having an amine-reactive functional group to reduce the ammonium cation content in the metal complex dye precursor (c) to obtain a metal complex dye (C). Step 2: A mixing step of mixing the first resin (A), the photoacid generator (B), and the metal complex dye (C) obtained in step 1.

[0027] <Process 1> Step 1 is a modification step in which a metal complex dye precursor (c) containing an ammonium cation is reacted with a compound having an amine-reactive functional group to obtain a metal complex dye (C) in which the ammonium cation content in the metal complex dye precursor (c) is reduced.

[0028] Metal complex dye precursors (c) containing ammonium cations are used as raw materials for metal complex dyes (C). The metal complex structure that functions as a dye in metal complex dye precursors (c) is essentially the same as that of metal complex dyes (C). A typical metal complex dye precursor (c) consists of a monoazo dye with a coordinating functional group such as a hydroxyl group, carboxyl group, or amino group, coordinated to a metal ion (such as chromium, copper, cobalt, nickel, or iron) and a countercation such as an ammonium cation. Metal complex dye precursors (c) are generally classified into two classes: 1:1 type metal complex dyes (one monoazo dye molecule coordinated to one metal atom) and 1:2 type metal complex dyes (two monoazo dye molecules coordinated to one metal atom). Monoazo dyes generally have one of the following structures: o,o'-dihydroxyazo, o-hydroxy-o'-aminoazo, or o-hydroxy-o'-carboxyazo. The metal complex dye precursor (c) can be used alone or in combination of two or more kinds.

[0029] The ammonium cation content (mass%) in the metal complex dye precursor (c) is determined by the following procedure. Methyl benzoate as an internal standard and tetrahydrofuran as a dilution solvent are added to the metal complex dye precursor (c), and a pretreatment agent for gas chromatography is added as needed to prepare a sample. The resulting sample is stirred and then analyzed by GC or GC-MS using the internal standard method to calculate the ammonium cation content (mass%). When two or more metal complex dye precursors (c) are combined, the ammonium cation content of the metal complex dye precursor (c) is determined by dividing the total mass of the ammonium cations in the two or more metal complex dye precursors (c) by the total mass of the two or more metal complex dye precursors (c). The ammonium cation content in the metal complex dye precursor (c) is preferably greater than 21 mass%.

[0030] The metal element forming the metal complex ion contained in the metal complex dye precursor (c) is preferably at least one selected from the group consisting of chromium, copper, cobalt, nickel, and iron, and more preferably chromium.

[0031] In the present disclosure, an "ammonium cation" is a compound represented by formula (8). R x R y NH2 + (8) (In equation (8), R x and R y each independently represents a hydrogen atom or an organic group.

[0032] An ammonium cation is a protonated amine compound that can react with a compound having an amine-reactive functional group. In the present disclosure, the amine compound also includes ammonia.

[0033] In equation (8), R x and R y The organic group represented by the formula (I) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 2 to 14 carbon atoms. The alkyl group may have a substituent. Examples of the substituent of the alkyl group include a hydroxyl group and an alkoxy group.

[0034] The ammonium cation represented by formula (8) is a protonated product of an alkylamine having 2 to 14 carbon atoms, which may have a hydroxyl group or an alkoxy group, and NH4 + It is preferable that the material is at least one selected from the group consisting of:

[0035] Specific examples of the ammonium cation represented by formula (8) include a protonated product of ethanolamine, a protonated product of diethanolamine, a protonated product of methoxypropylamine (CH3OC3H6NH2), a protonated product of octoxypropylamine (CH8H 17 OC3H6NH2) protonated compound, tetradecylamine (C 14 H29 NH2) protonated form, and NH4 + Examples include:

[0036] The metal complex dye precursor (c) contains Na in addition to the ammonium cation. + , Li + , K. + , H + Counter cations such as: These counter cations may be used alone or in combination of two or more.

[0037] Examples of the metal complex dye precursor (c) include black dyes defined by the color index (CI) of Solvent Black 22 to 47, blue dyes defined by the CI of Solvent Blue 44 and 137, yellow dyes defined by the CI of Solvent Yellow 13, 19, 21, 25, 25:1, 62, 79, 81, 82, 83, 83:1, 88, 89, 90, 151, and 161, orange dyes defined by the CI of Solvent Orange 5, 11, 20, 40:1, 41, 45, 54, 56, 58, 62, 70, 81, and 99, and solvent red 8, 35, and 83. Examples of dyes include red dyes specified by CIs of :1, 84:1, 90, 90:1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, and 243; purple dyes specified by CIs of Solvent Violet 2, 21, 21:1, 46, 49, 58, and 6; brown dyes specified by CIs of Solvent Brown 28, 42, 43, 44, 53, 62, and 63; and dyes specified by CIs of Acid Yellow 59, 121, Acid Orange 74, 162, and Acid Red 211.

[0038] The metal complex dye precursor (c) is preferably at least one selected from black dyes defined by the CIs of Solvent Black 22 to 47, and more preferably at least one selected from black dyes defined by the CIs of Solvent Black 27, 29, or 34. When the metal complex dye (C) obtained from the metal complex dye precursor (c) is used, the light-shielding properties of the coating of the cured positive photosensitive resin composition can be maintained.

[0039] Examples of the amine-reactive functional group in the compound having an amine-reactive functional group in Step 1 include an ester group, an acid anhydride group, an acyl halide group, a carboxy group, a carbonyl group, a cyano group, and a halogeno group. When an ester is used as the compound having an amine-reactive functional group in Step 1, an amide is produced by reaction with the ammonium cation in the metal complex dye precursor (c).

[0040] In step 1, the reaction between the ammonium cation in the metal complex dye precursor (c) and the compound having an amine-reactive functional group is preferably carried out in a solvent. Examples of the solvent include ether solvents such as diethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and tetrahydrofuran; alcohol solvents such as methanol, ethanol, isopropanol, butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and ε-caprolactam; and hydrocarbon solvents such as n-hexane, n-pentane, n-octane, methylcyclohexane, benzene, toluene, and xylene. The solvents can be used alone or in combination.

[0041] The solvent may be a compound having an amine-reactive functional group. Examples of solvents having an amine-reactive functional group include ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, ethyl lactate, ethyl butyrate, propylene glycol monomethyl ether acetate, diethyl carbonate, dimethyl carbonate, and γ-butyrolactone; nitrile solvents such as acetonitrile; and ketone solvents such as acetone, cyclopentanone, and cyclohexanone. Solvents having an amine-reactive functional group can be used alone or in combination. Among these, ester solvents such as ethyl lactate and γ-butyrolactone are preferred because they have a high ability to dissolve the metal complex dye precursor (c) and the solvent itself reacts gently with amines.

[0042] The amount of the solvent having an amine-reactive functional group used is generally 10 to 5,000 parts by mass, preferably 50 to 3,000 parts by mass, and more preferably 100 to 2,000 parts by mass, based on 100 parts by mass of the metal complex dye precursor (c). When the amount of the solvent having an amine-reactive functional group used is 10 parts by mass or more, the ammonia cation content can be effectively reduced by reaction with the ammonium cation in the metal complex dye precursor (c), thereby increasing the sensitivity of the chemically amplified photosensitive resin composition. When the amount of the solvent having an amine-reactive functional group used is 5,000 parts by mass or less, the solids concentration of the chemically amplified photosensitive resin composition can be maintained within an appropriate range when step 2 is performed without removing the solvent after step 1.

[0043] Examples of compounds having an amine-reactive functional group other than solvents having an amine-reactive functional group include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, and a mixed anhydride of acetic acid and butyric acid; aromatic carboxylic acid anhydrides such as benzoic anhydride, cinnamic anhydride, and salicylic anhydride; acid halides such as acetic acid chloride, propionic acid chloride, and benzoyl chloride; and silicon halides such as trimethylsilyl chloride, dimethylphenylsilyl chloride, triethylsilyl chloride, methyldiphenylsilyl chloride, tert-butyldimethylsilyl chloride, and triphenylsilyl chloride. aliphatic carbonyl compounds such as formaldehyde, acetaldehyde, and acetylacetone; aromatic carbonyl compounds such as benzaldehyde and salicylaldehyde; alkyl halide compounds such as methyl chloride, methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl chloride, isopropyl chloride, isopropyl iodide, butyl chloride, isobutyl chloride, isobutyl bromide, and isobutyl iodide; alkenyl halide compounds such as allyl chloride, allyl bromide, and allyl iodide; and alkynyl halide compounds such as propargyl chloride, propargyl bromide, propargyl iodide, 1-methylpropargyl chloride, and 1-methylpropargyl bromide.

[0044] The amount of the compound having an amine-reactive functional group other than the solvent used is generally 1 to 500 parts by mass, preferably 2 to 200 parts by mass, and more preferably 5 to 100 parts by mass, based on 100 parts by mass of the metal complex dye precursor (c).

[0045] The reaction time in step 1 is generally 0.01 hours or more, preferably 0.5 hours or more, and more preferably 2 hours or more.

[0046] The reaction temperature in step 1 is generally 0 to 200°C, preferably 10 to 150°C, and more preferably 20 to 120°C.

[0047] The degree of progress of the reaction between a compound having an amine-reactive functional group and an ammonium cation generally depends on both the reaction temperature and the reaction time. When the reaction temperature in Step 1 is 0°C or higher and lower than 20°C, the reaction time is preferably 1 hour to 40,000 hours, more preferably 3 hours to 30,000 hours. When the reaction temperature in Step 1 is 20°C or higher and lower than 60°C, the reaction time is preferably 1 hour to 30,000 hours, more preferably 2 hours to 20,000 hours. When the reaction temperature in Step 1 is higher than 60°C and lower than 120°C, the reaction time is preferably 0.1 hours to 800 hours, more preferably 0.3 hours to 500 hours. When the reaction temperature in Step 1 is higher than 120°C and lower than 200°C, the reaction temperature is preferably 0.01 hours to 100 hours, more preferably 0.02 hours to 30 hours.

[0048] Step 1 is preferably carried out in an atmosphere of air, oxygen gas, or nitrogen gas.

[0049] Step 1 may be carried out by stirring a solution containing the metal complex dye precursor (c) and the compound having an amine-reactive functional group, or by leaving the solution to stand.

[0050] Step 1 is preferably carried out by using a compound having an amine-reactive functional group as a solvent, dissolving the metal complex dye precursor (c) in the solvent, and stirring or leaving the mixture to stand. Using a compound having an amine-reactive functional group as a solvent can facilitate the operation of Step 1.

[0051] The metal complex dye (C) obtained by reducing the ammonium cation content in the metal complex dye precursor (c) in step 1 may be used in solution form in step 2. Alternatively, the metal complex dye (C) may be extracted in a solid state by a method such as recrystallization or reprecipitation, or the solution containing the metal complex dye (C) may be concentrated to a desired concentration using a rotary evaporator or the like.

[0052] <Process 2> Step 2 is a mixing step in which the first resin (A), the photoacid generator (B), and the metal complex dye (C) obtained in step 1 are mixed. Details of the first resin (A), the photoacid generator (B), and the metal complex dye (C) will be described later. The first resin (A) and the photoacid generator (B) may be mixed as powders and then dissolved in a solvent, or one or both may be dissolved in a solvent to form a solution of the desired concentration and then mixed. Typical mixing devices that can be used include a reaction vessel equipped with a stirring bath, a three-one motor, a magnetic stirrer, a ball mill, a mix rotor, an ultrasonic mixer, a bead mill, and a Filmix disperser.

[0053] [Positive-type photosensitive resin composition] A positive photosensitive resin composition according to one embodiment includes a first resin (A) having a plurality of alkali-soluble functional groups, at least some of which are protected with acid-decomposable groups, a photoacid generator (B), and a metal complex dye (C).

[0054] <First Resin (A)> The first resin (A) is not particularly limited as long as it has a plurality of alkali-soluble functional groups, at least some of which are protected with acid-decomposable groups. Examples of alkali-soluble functional groups include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group. Among these, the alkali-soluble functional group is preferably a carboxy group or a phenolic hydroxyl group, and more preferably a phenolic hydroxyl group.

[0055] Since some of the alkali-soluble functional groups are protected with acid-decomposable groups, the alkali solubility of the first resin (A) before exposure is suppressed. The first resin (A) may have alkali-soluble functional groups other than the alkali-soluble functional groups protected with acid-decomposable groups.

[0056] In the presence of acid generated during exposure, post-exposure baking (PEB) is optionally performed to promote decomposition (deprotection) of the acid-decomposable groups and regenerate alkali-soluble functional groups. This promotes alkali dissolution of the first resin (A) in the exposed areas during development. The first resin (A) can be used alone or in combination of two or more types. For example, the first resin (A) may be a combination of two or more resins that differ in the polymer structural unit, acid-decomposable group, protection rate of alkali-soluble functional groups, or combination thereof.

[0057] (Protection of alkali-soluble functional groups by acid-decomposable groups) The first resin (A) can be obtained by protecting some of the alkali-soluble functional groups of a base resin (a) having a plurality of alkali-soluble functional groups with acid-decomposable groups. For example, when the alkali-soluble functional groups are phenolic hydroxyl groups, the first resin (A) having phenolic hydroxyl groups protected with acid-decomposable groups can be obtained by the reaction of Ar-OR 5 Ar represents an aromatic ring derived from phenol, and R 5 represents an acid-decomposable group.

[0058] The acid-decomposable group is a group that is decomposed (deprotected) in the presence of an acid, if necessary by heating, to generate an alkali-soluble functional group. Specific examples include groups having a tertiary alkyl group such as a tert-butyl group, a 1,1-dimethylpropyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 1-methyladamantyl group, a 1-ethyladamantyl group, a tert-butoxycarbonyl group, and a 1,1-dimethylpropoxycarbonyl group; silyl groups such as a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a tert-butyldiphenylsilyl group; and groups represented by the formula (4): -CR 6 R 7 -OR 8 (4) (In formula (4), R 6 and R 7are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 8 is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, or R 6 or R 7 One of the two and R 8 may be bonded to form a ring structure having 3 to 10 ring members, and R 6 , R 7 , and R 8 may be substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine, and iodine. The group represented by formula (4) forms an acetal structure or a ketal structure together with the oxygen atom derived from the alkali-soluble functional group when the alkali-soluble functional group is an alcoholic hydroxyl group or a phenolic hydroxyl group. These acid-decomposable groups may be used alone or in combination of two or more.

[0059] The acid-decomposable group is preferably a group represented by formula (4), since this allows a photosensitive resin composition with high sensitivity to be obtained even at a low exposure dose. 6 and R 7 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 8is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, each of which may be substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine, and iodine. Examples of such acid-decomposable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl, and 1-(2-cyclohexylethoxy)ethyl groups, with 1-ethoxyethyl and 1-n-propoxyethyl groups being preferred. Examples of acid-decomposable groups include a group represented by formula (4), in which R 6 or R 7 One of the two and R 8 and R bonded to form a ring structure having 3 to 10 ring members can also be suitably used. In this case, R not involved in the formation of the ring structure can be used. 6 or R 7 is preferably a hydrogen atom. Examples of such an acid-decomposable group include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with a 2-tetrahydrofuranyl group being preferred.

[0060] The protection reaction of the alkali-soluble functional group can be carried out using a common protecting agent under known conditions. For example, the first resin (A) can be obtained by reacting the base resin (a) of the first resin (A) with the protecting agent in the presence of an acid or a base at a reaction temperature of −20 to 50° C. without a solvent or in a solvent such as toluene or hexane.

[0061] Known protecting agents capable of protecting alkali-soluble functional groups can be used as the protecting agent. For example, isobutene can be used when the acid-decomposable group is a tert-butyl group, and di-tert-butyl dicarbonate can be used when the acid-decomposable group is a tert-butoxycarbonyl group. When the acid-decomposable group is a silyl group such as a trimethylsilyl group or a triethylsilyl group, silicon-containing chlorides such as trimethylsilyl chloride and triethylsilyl chloride, or silicon-containing triflate compounds such as trimethylsilyl triflate and triethylsilyl triflate can be used. When the acid-decomposable group is a methoxymethyl group, chloromethyl methyl ether can be used; when the acid-decomposable group is a 1-ethoxyethyl group, ethyl vinyl ether can be used; when the acid-decomposable group is a 1-n-propoxyethyl group, n-propyl vinyl ether can be used; when the acid-decomposable group is a 2-tetrahydrofuranyl group, 2,3-dihydrofuran can be used; and when the acid-decomposable group is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran can be used.

[0062] Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid. Salts of organic acids, such as pyridinium salts of p-toluenesulfonic acid, can also be used as acid sources. Examples of bases include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, metal hydrides such as sodium hydride, and amine compounds such as pyridine, N,N-dimethyl-4-aminopyridine, imidazole, triethylamine, and diisopropylethylamine.

[0063] In another embodiment, the first resin (A) can be obtained by protecting at least a portion or all of the alkali-soluble functional groups of a polymerizable monomer having one or more alkali-soluble functional groups with acid-decomposable groups, and then polymerizing or copolymerizing the polymerizable monomer having the alkali-soluble functional group protected with the acid-decomposable group and, if necessary, other polymerizable monomers. The alkali-soluble functional groups of the polymerizable monomer having the alkali-soluble functional group can be protected by the same method as that used for protecting the alkali-soluble functional group of the base resin (a).

[0064] (Base resin (a)) Examples of the base resin (a) of the first resin (A) include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenolic resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins, all of which have multiple alkali-soluble functional groups. For example, derivatives of phenolic resins include polyalkenylphenolic resins in which an alkenyl group is bonded to a benzene ring, and derivatives of polystyrene resins include hydroxypolystyrene resin derivatives in which a phenolic hydroxyl group and a hydroxyalkyl group or alkoxy group are bonded to a benzene ring. Homopolymers or copolymers of polymerizable monomers having alkali-soluble functional groups can also be used as the base resin (a). These base resins (a) can be used alone or in combination of two or more.

[0065] The base resin (a) may have a radically polymerizable functional group. In one embodiment, the base resin (a) has a (meth)acryloyloxy group, an allyl group, or a methallyl group as the radically polymerizable functional group.

[0066] (Copolymer (a1) of polymerizable monomer having alkali-soluble functional group and other polymerizable monomer) In one embodiment, the base resin (a) of the first resin (A) is a copolymer (a1) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, and the copolymer (a1) has multiple alkali-soluble functional groups. In this embodiment, the first resin (A) is copolymer (a1) in which at least a portion of the multiple alkali-soluble functional groups are protected with an acid-decomposable group. The copolymer (a1) may have two or more types of alkali-soluble functional groups.

[0067] Examples of the polymerizable functional group possessed by the polymerizable monomer include radically polymerizable functional groups, such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, and -OC-CH=CH-CO-.

[0068] The copolymer (a1) can be produced, for example, by radical polymerization of a polymerizable monomer having an alkali-soluble functional group with another polymerizable monomer. After synthesizing the copolymer by radical polymerization, the alkali-soluble functional group may be added to the copolymer.

[0069] Examples of polymerizable monomers having an alkali-soluble functional group include maleic acid derivatives such as maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, and maleic anhydride; acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; and unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid; 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, and 3-hydroxypropyl(meth)acrylate. polymerizable monomers having an alcoholic hydroxyl group, such as 4-hydroxystyrene, 4-hydroxyphenyl(meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, 4-hydroxyphenylmaleimide; polymerizable monomers having a sulfo group, such as (meth)allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid; polymerizable monomers having a phosphate group, such as mono(2-(meth)acryloyloxyethyl)phosphate; and polymerizable monomers having an acid anhydride group, such as itaconic anhydride, citraconic anhydride. Examples of other polymerizable monomers include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; (meth)acrylic acid esters such as alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and isobornyl (meth)acrylate; and N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide.

[0070] From the viewpoint of heat resistance, etc., the copolymer (a1) preferably has one or more types of cyclic structures such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, a heterocyclic structure, etc. From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably an acrylic acid derivative or a polymerizable monomer having a phenolic hydroxyl group, more preferably a polymerizable monomer having a phenolic hydroxyl group.

[0071] As a polymerizable monomer having a phenolic hydroxyl group, after polymerization, the following formula (1) [ka] In formula (1), it is preferable to form a structural unit represented by the formula: 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.

[0072] In formula (1), R 1 is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, more preferably 1. As such a polymerizable monomer having a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferred.

[0073] Other polymerizable monomers include those represented by the formula (2) after polymerization. [ka] In formula (2), it is preferable to form a structural unit represented by the formula: 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0074] In equation (2), R 2 and R 3 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. 4 is preferably a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

[0075] In one embodiment, the copolymer (a1) has the formula (1) [ka] (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. and a structural unit represented by formula (2) [ka] (In formula (2), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. It has a structural unit represented by the following formula:

[0076] In the copolymer (a1), the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) is preferably formula (1):formula (2)=70-95:30-5, and more preferably formula (1):formula (2)=75-90:25-10.

[0077] It is particularly preferred to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having a phenolic hydroxyl group and phenylmaleimide or N-cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radical polymerization of these polymerizable monomers, shape retention and developability can be improved, and outgassing can be reduced.

[0078] Examples of the polymerization initiator used in producing the base resin (a) or the copolymer (a1) by radical polymerization include, but are not limited to, azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN); dicumyl peroxide, 2,5-dimethyl-2,5-di( Peroxide polymerization initiators having a 10-hour half-life temperature of 100 to 170°C, such as tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide; or peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, and tert-butylperoxypivalate can be used.

[0079] The amount of the polymerization initiator used is preferably 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, and is preferably 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, relative to 100 parts by mass of the total of the polymerizable monomers.

[0080] A RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. The RAFT agent may be a thiocarbonylthio compound, such as, but not limited to, dithioesters, dithiocarbamates, trithiocarbonates, and xanthates.

[0081] The RAFT agent can be used in the range of 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the total of the polymerizable monomers.

[0082] The weight-average molecular weight (Mw) of the base resin (a) or copolymer (a1) can be 3,000 to 80,000, preferably 4,000 to 70,000, and more preferably 5,000 to 60,000. The number-average molecular weight (Mn) can be 1,000 to 30,000, preferably 1,500 to 25,000, and more preferably 2,000 to 20,000. The polydispersity (Mw / Mn) can be 1.0 to 3.5, preferably 1.1 to 3.0, and more preferably 1.2 to 2.8. By setting the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (Mw / Mn) within the above ranges, a positive-type photosensitive resin composition with excellent alkali solubility and developability can be obtained.

[0083] In one embodiment, 1 mol % to 99 mol %, preferably 3 mol % to 98 mol %, and more preferably 5 mol % to 97 mol % of the alkali-soluble functional groups in the first resin (A) are protected with acid-decomposable groups. By setting the proportion of alkali-soluble functional groups protected with acid-decomposable groups in the first resin (A) to 1 mol % or more, chemical amplification functionality can be imparted to the photosensitive resin composition, thereby achieving high sensitivity. By setting the proportion of alkali-soluble functional groups protected with acid-decomposable groups to 99 mol % or less, the amount of remaining acid-decomposable groups that do not react during exposure can be reduced, thereby increasing the solubility of the exposed area and achieving high sensitivity. The proportion of alkali-soluble functional groups protected with acid-decomposable groups can be calculated from the weight loss rate (%) of the first resin (A) measured using a thermogravimetric differential thermal analyzer (TG / DTA). In the present disclosure, when the first resin (A) is a combination of two or more resins differing in protection rate and / or acid-decomposable group, the protection rate of the alkali-soluble functional group in the first resin (A) is a value when the two or more resins are regarded as a single first resin (A) as a whole.

[0084] The first resin (A) is a compound represented by the formula (3): [ka] (In formula (3), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 5 is an acid-decomposable group, r is an integer of 0 to 5, and s is an integer of 0 to 5, with the proviso that r+s is an integer of 1 to 5. It is preferable that the compound has a structural unit represented by formula (3), and has at least one structural unit represented by formula (3) in which s is an integer of 1 or more. 5 The acid-decomposable group is a group having a tertiary alkyl group, and a group represented by the formula (4) -CR 6 R 7 -OR 8 (4) It is preferable that the group is any one selected from the groups represented by the following formula:

[0085] Examples of the group having a tertiary alkyl group include a tert-butyl group, a 1,1-dimethyl-propyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 1-methyladamantyl group, a 1-ethyladamantyl group, a tert-butoxycarbonyl group, a 1,1-dimethyl-propoxycarbonyl group, etc. As the group having a tertiary alkyl group, a tert-butoxycarbonyl group is preferred.

[0086] In equation (4), R 6 and R 7 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 8 is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, or R 6 or R 7 One of the two and R 8 may be bonded to form a ring structure having 3 to 10 ring members, and R 6 , R 7 , and R 8 may be substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

[0087] In equation (4), R 6 and R 7 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 8 is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine, and iodine.

[0088] Examples of such acid-decomposable groups include 1-alkoxyalkyl groups, such as methoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl, and 1-(2-cyclohexylethoxy)ethyl groups, with 1-ethoxyethyl and 1-n-propoxyethyl groups being preferred.

[0089] A group represented by formula (4), R 6 or R 7 One of the two and R 8 Examples of the acid-decomposable group in which the above are bonded to form a ring structure having 3 to 10 ring members include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with a 2-tetrahydrofuranyl group being preferred.

[0090] The first resin (A) is a compound represented by the formula (2): [ka] (In formula (2), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0091] In equation (2), R 2 and R 3 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. 4is preferably a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group.

[0092] In one embodiment, the number of structural units represented by formula (3) where s is an integer of 1 or greater, i.e., structural units represented by formula (3) in which at least one alkali-soluble functional group is protected with an acid-decomposable group, is 1% to 95%, preferably 2% to 90%, and more preferably 4% to 85% of the total number of structural units in the first resin (A). By setting the proportion of these structural units to 1% or greater, a chemical amplification function can be imparted to the photosensitive resin composition, thereby achieving high sensitivity. By setting the proportion of these structural units to 95% or less, the amount of unreacted acid-decomposable groups remaining can be reduced, and the solubility of exposed areas can be increased, thereby achieving high sensitivity. When the first resin (A) is a combination of two or more resins differing in protection rate and / or acid-decomposable group, the proportion of the above structural units refers to the proportion of structural units represented by formula (3) where s is an integer of 1 or greater in one resin.

[0093] In one embodiment, the positive photosensitive resin composition contains 1% by mass to 80% by mass, preferably 2% by mass to 65% by mass, and more preferably 3% by mass to 50% by mass of the first resin (A) based on 100% by mass of the solid content. When the content of the first resin (A) is 1% by mass or more based on 100% by mass of the solid content, the photosensitive resin composition is imparted with a chemical amplification function, thereby achieving high sensitivity. When the content of the first resin (A) is 80% by mass or less based on 100% by mass of the solid content, the amount of unreacted acid-decomposable groups remaining is reduced, and the solubility of the exposed area is increased, thereby achieving high sensitivity.

[0094] <Photoacid generator (B)> The positive-type photosensitive resin composition contains a photoacid generator (B). The photoacid generator (B) is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, gamma rays, or electron beams. The photoacid generator (B) promotes decomposition of the acid-decomposable groups in the first resin (A) to regenerate alkali-soluble functional groups, thereby increasing the alkali solubility of the first resin (A). Furthermore, the presence of the acid generated from the photoacid generator (B) in the irradiated area makes the resin in that area more easily dissolve in an alkaline aqueous solution together with the acid. As a result, high-sensitivity, high-resolution patterns can be formed even with low exposure doses. The photoacid generator (B) can be used alone or in combination of two or more types.

[0095] In one embodiment, the positive photosensitive resin composition contains 1% by mass to 50% by mass, preferably 2% by mass to 40% by mass, and more preferably 3% by mass to 30% by mass of the photoacid generator (B) based on 100% by mass of the solid content. When the content of the photoacid generator (B) is 1% by mass or more based on 100% by mass of the solid content, high sensitivity can be achieved. When the content of the photoacid generator (B) is 50% by mass or less based on 100% by mass of the solid content, good alkali developability can be achieved.

[0096] In one embodiment, the positive-type photosensitive resin composition contains a quinone diazide compound as the photoacid generator (B). When irradiated with radiation such as visible light, ultraviolet light, gamma rays, or electron beams, the quinone diazide compound generates an alkali-soluble carboxylic acid compound via the reaction shown in Reaction Scheme 1 below. The generated carboxylic acid compound promotes decomposition of the acid-decomposable groups in the first resin (A) to regenerate alkali-soluble functional groups, thereby increasing the alkali solubility of the first resin (A). Before exposure, the quinone diazide compound interacts (e.g., forms hydrogen bonds) with functional groups of a binder resin such as a novolac resin, rendering the binder resin insoluble in an alkaline aqueous solution. Meanwhile, the presence of the alkali-soluble carboxylic acid compound in the irradiated area facilitates the dissolution of the resin in that area, along with the carboxylic acid compound, in an alkaline aqueous solution. Furthermore, the carboxylic acid compound has a relatively larger molecular structure than acids generated from photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is therefore less likely to diffuse in a coating. As a result of the synergistic action of these, the difference in alkali solubility between the unexposed and exposed areas can be increased, thereby enabling the formation of a high-resolution pattern with high sensitivity even at a low exposure dose.The quinone diazide compounds can be used alone or in combination of two or more.

[0097] [ka]

[0098] In one embodiment, high-resolution patterns can be formed without the post-exposure bake (PEB) required for typical chemically amplified resists. The quinone diazide compound has a relatively high quantum yield, efficiently generating a carboxylic acid compound in the exposed area. When an acid-labile group capable of being decomposed by a carboxylic acid compound is present in the vicinity, the generated carboxylic acid compound decomposes the acid-labile group even at room temperature, regenerating an alkali-soluble functional group, thereby increasing the difference in alkali solubility between the unexposed and exposed areas. By omitting PEB, deterioration of pattern formability due to excessive diffusion of acid generated from the photoacid generator to the unexposed area in the high-temperature environment during PEB can be suppressed. Furthermore, when a resin having an epoxy group and a phenolic hydroxyl group (described below) is used as an optional component, omitting PEB prevents ring-opening polymerization of the epoxy group in the resin having an epoxy group and a phenolic hydroxyl group, thereby maintaining the alkali solubility of the resin having an epoxy group and a phenolic hydroxyl group during development.

[0099] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond or a sulfonamide bond. From the viewpoint of contrast between exposed and unexposed areas, it is preferred that 20 mol % or more of the total functional groups of the polyhydroxy compound or polyamino compound be substituted with quinone diazide.

[0100] Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Tyrol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TM Examples of suitable phenols include, but are not limited to, L-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all trade names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (all trade names, Asahi Organic Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.).

[0101] Examples of polyamino compounds include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0102] Polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

[0103] The quinone diazide compound is preferably a 1,2-naphthoquinone diazide-4-sulfonic acid ester or a 1,2-naphthoquinone diazide-5-sulfonic acid ester of a polyhydroxy compound.

[0104] In one embodiment, the positive photosensitive resin composition contains a quinone diazide compound in an amount of 1% by mass to 50% by mass, preferably 2% by mass to 40% by mass, and more preferably 3% by mass to 30% by mass, based on 100% by mass of the solid content. When the content of the quinone diazide compound is 1% by mass or more, based on 100% by mass of the solid content, high sensitivity can be achieved. When the content of the quinone diazide compound is 50% by mass or less, based on 100% by mass of the solid content, good alkaline developability can be achieved.

[0105] The photoacid generator (B) other than a quinone diazide compound is preferably one that generates an acid having a pKa of 4 or less upon irradiation, more preferably one that generates an acid having a pKa of 3 or less. Such a photoacid generator (B) can generate an acid capable of decomposing an acid-decomposable group.

[0106] As the photoacid generator (B) other than a quinone diazide compound, one that generates an acid having a pKa of −15 or more upon irradiation with radiation is preferred, and one that generates an acid having a pKa of −5 or more is more preferred. When an optional resin having an epoxy group and a phenolic hydroxyl group, which can become the second resin (D) described below, is present during exposure and post-exposure bake (PEB), such a photoacid generator (B) can maintain the alkali solubility of the resin having an epoxy group and a phenolic hydroxyl group during development without excessively promoting ring-opening polymerization of the epoxy group.

[0107] Examples of such photoacid generators (B) include trichloromethyl-s-triazine compounds, onium salts such as sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, oxime sulfonate compounds are preferred because of their high sensitivity and insulating properties.

[0108] An example of the oxime sulfonate compound is a compound represented by formula (5). [ka]

[0109] In equation (5), R 9 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom; R 10 and R 11 R are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, an acyloxy group, a carboxy group, an alkoxycarbonyl group, or a fluoroalkyl group. 10 and R 11 may be bonded to form a ring structure. The ring structure preferably has 3 to 10 ring members.

[0110] R 9 Examples of the substituted or unsubstituted alkyl group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms, and a methyl group, an ethyl group, or an n-propyl group is preferred.

[0111] R 9 The substituted or unsubstituted alkoxy group includes, for example, a linear alkoxy group having 1 to 5 carbon atoms or a branched alkoxy group having 3 to 5 carbon atoms, and is preferably a methoxy group or an ethoxy group.

[0112] R 9Examples of the substituents on the alkyl and alkoxy groups include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), cyano groups, nitro groups, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms.

[0113] R 9 The alkyl group substituted by the formula (I) is preferably a fluoroalkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group, and even more preferably a trifluoromethyl group.

[0114] R 9 The substituted or unsubstituted aryl group includes, for example, an aryl group having 6 to 20 carbon atoms, and is preferably a phenyl group, a 4-methylphenyl group, or a naphthyl group.

[0115] R 9 Examples of the substituent on the aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

[0116] R 9 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0117] R 10 and R 11 The substituted or unsubstituted aryl group includes, for example, an aryl group having 6 to 20 carbon atoms, and is preferably a phenyl group or a naphthyl group.

[0118] R 10 and R 11 Examples of the substituted or unsubstituted heterocyclic group include a 2-benzofuranyl group, a 3-benzofuranyl group, a 2-benzimidazolyl group, a 2-benzoxazolyl group, a 2-benzothiazolyl group, a 2-indolyl group, a 3-coumarinyl group, a 4-coumarinyl group, a 3-isocoumarinyl group, and a 4-isocoumarinyl group.

[0119] R 10 and R 11 Examples of the substituents on the aryl group and heterocyclic group include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acyloxy groups having 2 to 4 carbon atoms, and halogen atoms (fluorine atom, chlorine atom, bromine atom, and iodine atom).

[0120] R 10 and R 11 Examples of the acyloxy group of R include an acetoxy group and a benzoyl group. 10 and R 11 The alkoxycarbonyl group includes, for example, an ethoxycarbonyl group.

[0121] R 10 and R 11 Examples of the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.

[0122] R 10 is preferably a cyano group, a carboxy group, an alkoxycarbonyl group, or a fluoroalkyl group, and more preferably a cyano group or a trifluoromethyl group.

[0123] R 11 is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and is preferably a 4-methoxyphenyl group, or a substituted or unsubstituted 2-benzofuranyl group, 3-benzofuranyl group, 3-coumarinyl group, 4-coumarinyl group, 3-isocoumarinyl group, or 4-isocoumarinyl group.

[0124] R 10 and R 11 Examples of the oxime sulfonate compound having a ring structure formed by bonding include oxime sulfonate compounds represented by formula (5a). [ka]

[0125] In formula (5a), R 9 is as explained in equation (5), and R 12 are each independently an alkyl group, an alkoxy group, or a halogen atom, and m represents an integer of 0 to 5.

[0126] R 12 Examples of the alkyl group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms, and a methyl group, an ethyl group, or an n-propyl group is preferred.

[0127] R 12 Examples of the alkoxy group include a linear alkoxy group having 1 to 5 carbon atoms and a branched alkoxy group having 3 to 5 carbon atoms, and a methoxy group or an ethoxy group is preferred.

[0128] R 12 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a fluorine atom is preferred. m is preferably 0 or 1.

[0129] Examples of oxime sulfonate compounds include (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 2-[2-(propylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, and 2-[2-(4-methylphenylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile.

[0130] In one embodiment, the positive photosensitive resin composition contains 0.5% by mass to 50% by mass, preferably 1% by mass to 40% by mass, and more preferably 2% by mass to 30% by mass of a photoacid generator (B) other than a quinone diazide compound, based on 100% by mass of the solid content. When the content of the photoacid generator (B) other than a quinone diazide compound is 0.5% by mass or more based on 100% by mass of the solid content, high sensitivity can be achieved. When the content of the photoacid generator (B) other than a quinone diazide compound is 50% by mass or less based on 100% by mass of the solid content, alkaline developability is good.

[0131] <Metal complex dyes (C)> The positive-type photosensitive resin composition contains a metal complex dye (C). Compared to pigments, the metal complex dye (C) leaves less residue during development, making it possible to form high-resolution patterns in a coating. The metal complex dye (C) is also easily soluble in organic solvents and is less likely to precipitate in solution even when incorporated at high concentrations. Furthermore, it is less likely to fade during heat treatment after exposure, making it possible to efficiently increase the optical density (OD value) of the cured coating. The metal complex dye (C) can be used alone or in combination of two or more types.

[0132] The metal complex dye (C) is obtained by reacting the metal complex precursor (c) with a compound having an amine-reactive functional group in step 1 of the above-described method for producing a positive-tone photosensitive resin composition, thereby reducing the ammonium cation content in the metal complex dye precursor (c). Without being bound by any theory, when the ammonium cation content in the metal complex dye (C) is high, the ammonium cations are deprotonated to produce a large amount of amine, which caps alkali-soluble functional groups, such as phenolic hydroxyl groups, in the positive-tone photosensitive resin composition. This capping reduces the alkali solubility of the exposed area of ​​the positive-tone photosensitive resin composition. As a result, the difference in solubility between the unexposed and exposed areas becomes smaller, and the sensitivity of the positive-tone photosensitive resin composition decreases. According to the present disclosure, a highly sensitive positive-tone photosensitive resin composition can be provided by reducing the ammonium cation content in the metal complex dye (C).

[0133] The ammonium cation content of the metal complex dye (C) is preferably 21% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less. By adjusting the ammonium cation content of the metal complex dye (C) to 21% by mass or less, the sensitivity of the positive-type photosensitive resin composition can be further increased. The ammonium cation content of the metal complex dye (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 6% by mass or more, and particularly preferably 10% by mass or more. By adjusting the ammonium cation content of the metal complex dye (C) to 0.5% by mass or more, the stability of the metal complex dye (C) in the positive-type photosensitive resin composition and its coating can be further increased. The ammonium cation content (% by mass) in the metal complex dye (C) is determined by the same procedure as the ammonium cation content (% by mass) in the metal complex precursor (c) described above.

[0134] The metal element forming the metal complex ion contained in the metal complex dye (C) is preferably at least one selected from the group consisting of chromium, copper, cobalt, nickel, and iron, and more preferably chromium.

[0135] The ammonium cation contained in the metal complex dye (C) may be any of those listed in the formula (8). The ammonium cation may be a proton adduct of an alkylamine having 2 to 14 carbon atoms, which may have a hydroxyl group or an alkoxy group, and NH4 + Specifically, the proton adduct of ethanolamine, the proton adduct of diethanolamine, the proton adduct of methoxypropylamine (CH3OC3H6NH2), the proton adduct of octoxypropylamine (CH8H ... 17 OC3H6NH2) protonated compound, tetradecylamine (C 14 H 29 NH2) protonated form, and NH4 + Examples include:

[0136] Metal complex dyes (C) contain Na in addition to ammonium cations.+ , Li + , K. + , H + Counter cations such as: These counter cations may be used alone or in combination of two or more.

[0137] Examples of the metal complex dye (C) include black dyes specified by the color index (CI) of Solvent Black 22 to 47, blue dyes specified by the CI of Solvent Blue 44 and 137, yellow dyes specified by the CI of Solvent Yellow 13, 19, 21, 25, 25:1, 62, 79, 81, 82, 83, 83:1, 88, 89, 90, 151, and 161, orange dyes specified by the CI of Solvent Orange 5, 11, 20, 40:1, 41, 45, 54, 56, 58, 62, 70, 81, and 99, and solvent red 8, 35, 83:1, 84:1, 90, 90:1, and 9 Examples of the dyes include red dyes specified by CIs of 1, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, and 243, purple dyes specified by CIs of Solvent Violet 2, 21, 21:1, 46, 49, 58, and 6, brown dyes specified by CIs of Solvent Brown 28, 42, 43, 44, 53, 62, and 63, and dyes specified by CIs of Acid Yellow 59, 121, Acid Orange 74, 162, and Acid Red 211, and the like, which have a reduced ammonium cation content in the metal complex dye.

[0138] The metal complex dye (C) preferably corresponds to at least one selected from the black dyes defined by the CIs of Solvent Black 22 to 47, and more preferably corresponds to at least one selected from the black dyes defined by the CIs of Solvent Black 27, 29, or 34. When the metal complex dye (C) is used, the light-shielding properties of the coating of the cured positive photosensitive resin composition can be maintained.

[0139] In one embodiment, the positive photosensitive resin composition contains 10% by mass to 60% by mass, preferably 15% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass of the metal complex dye (C) based on 100% by mass of the solids content. When the content of the metal complex dye (C) is 10% by mass or more based on 100% by mass of the solids content, the light-blocking properties of the cured coating can be maintained. When the content of the metal complex dye (C) is 60% by mass or less based on the total 100% by mass, the coating can be colored without impairing alkaline developability.

[0140] <Second resin (D)> The positive photosensitive resin composition may further contain a second resin (D). The second resin (D) is a resin different from the first resin (A) and does not have an alkali-soluble functional group protected by an acid-decomposable group.

[0141] The second resin (D) is not particularly limited, but preferably has an alkali-soluble functional group and is alkali-soluble. Examples of the alkali-soluble functional group include, but are not limited to, a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphate group, and a mercapto group. A second resin (D) having two or more types of alkali-soluble functional groups may be used.

[0142] Examples of the second resin (D) include homopolymers or copolymers of polymerizable monomers having alkali-soluble functional groups, and resins having epoxy groups and phenolic hydroxyl groups. Other examples of the second resin (D) include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenolic resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins, as well as resins to which alkali-soluble functional groups are bonded. Examples of derivatives of phenolic resins include polyalkenylphenolic resins in which an alkenyl group is bonded to a benzene ring, and examples of derivatives of polystyrene resins include hydroxypolystyrene resin derivatives in which a phenolic hydroxyl group and a hydroxyalkyl group or an alkoxy group are bonded to a benzene ring. These resins can be used alone or in combination of two or more.

[0143] The second resin (D) may have a radically polymerizable functional group. In one embodiment, the second resin (D) has a (meth)acryloyloxy group, an allyl group, or a methallyl group as the radically polymerizable functional group.

[0144] In one embodiment, the second resin (D) comprises a copolymer (a1) of the above-mentioned polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, which can be used as the base resin (a) of the first resin (A). The copolymer (a1) as the second resin (D) and the copolymer (a1) as the base resin (a) of the first resin (A) may be the same or different in one or more of their number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn), as well as the type and mass ratio of the polymerizable monomers constituting them.

[0145] In one embodiment, the second resin (D) is a compound represented by formula (1): [ka] (In formula (1), R 1is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. and a structural unit represented by formula (2) [ka] (In formula (2), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The copolymer (a1) has a structural unit represented by the following formula:

[0146] In one embodiment, the second resin (D) comprises a resin having an epoxy group and a phenolic hydroxyl group. The resin having an epoxy group and a phenolic hydroxyl group is an alkaline aqueous solution-soluble resin. The resin having an epoxy group and a phenolic hydroxyl group may have an alkali-soluble functional group other than the phenolic hydroxyl group. The resin having an epoxy group and a phenolic hydroxyl group can be obtained, for example, by reacting some of the epoxy groups of a compound having at least two epoxy groups per molecule (hereinafter sometimes referred to as an "epoxy compound") with the carboxyl group of a hydroxybenzoic acid compound. The epoxy groups of the resin having an epoxy group and a phenolic hydroxyl group react with the phenolic hydroxyl groups to form crosslinks during heat treatment (post-baking) after development, thereby improving the chemical resistance, heat resistance, etc. of the coating. Since the phenolic hydroxyl group contributes to solubility in an alkaline aqueous solution during development, the resin having an epoxy group and a phenolic hydroxyl group also functions as a dissolution promoter for the first resin (A) whose acid-decomposable group is not sufficiently decomposed (deprotected) when exposed to a low exposure dose, thereby making it possible to impart high sensitivity to the photosensitive resin composition.

[0147] The following reaction formula 2 shows an example of a reaction in which one of the epoxy groups of an epoxy compound reacts with the carboxy group of a hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group. [ka]

[0148] Examples of compounds having at least two epoxy groups per molecule include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol epoxy resins, biphenol epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds may contain two or more epoxy groups per molecule, and may be used alone or in combination of two or more. Because these compounds are thermosetting, it is common knowledge among those skilled in the art that their structures cannot be unambiguously described due to differences in the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, and the like.

[0149] An example of the structure of a novolac epoxy resin is shown in formula (6). In formula (6), for example, R 13 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a hydroxyl group, and n is an integer of 1 to 50. [ka]

[0150] Examples of phenol novolac epoxy resins include EPICLON (registered trademark) N-770 (DIC Corporation) and jER (registered trademark)-152 (Mitsubishi Chemical Corporation). Examples of cresol novolac epoxy resins include EPICLON (registered trademark) N-695 (DIC Corporation) and EOCN (registered trademark)-102S (Nippon Kayaku Co., Ltd.). Examples of bisphenol epoxy resins include bisphenol A epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (Mitsubishi Chemical Corporation), and YD-128 (trade name, Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F epoxy resins such as jER (registered trademark) 806 (Mitsubishi Chemical Corporation) and YDF-170 (trade name, Nippon Steel Chemical & Material Co., Ltd.). Examples of biphenol-type epoxy resins include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include NC-7000 (trade name, Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, DIC Corporation). Examples of alicyclic epoxy resins include EHPE (registered trademark)-3150 (Daicel Chemical Industries, Ltd.). Examples of heterocyclic epoxy resins include TEPIC (registered trademark), TEPIC-L, TEPIC-H, and TEPIC-S (Nissan Chemical Industries, Ltd.).

[0151] The compound having at least two epoxy groups per molecule is preferably a novolac epoxy resin, more preferably at least one selected from the group consisting of phenol novolac epoxy resins and cresol novolac epoxy resins. A positive photosensitive resin composition containing a resin having an epoxy group and a phenolic hydroxyl group derived from a novolac epoxy resin has excellent pattern formability, easy adjustment of alkali solubility, and little outgassing.

[0152] The hydroxybenzoic acid compound is a compound in which at least one of the 2- to 6-positions of benzoic acid is substituted with a hydroxyl group, and examples thereof include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, and 4-hydroxy-3-nitrobenzoic acid. Dihydroxybenzoic acid compounds are preferred in terms of enhancing alkaline developability. The hydroxybenzoic acid compounds can be used alone or in combination of two or more.

[0153] In one embodiment, the resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid compound, and is represented by the formula (7): [ka] In formula (7), b is an integer of 1 to 5, and * represents a bond to a residue other than the epoxy group involved in the reaction of a compound having at least two epoxy groups in one molecule.

[0154] In a method for obtaining a resin having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound can be used relative to 1 equivalent of the epoxy group of the epoxy compound, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. If the amount of the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if the amount is 1.0 equivalent or less, an increase in molecular weight due to side reactions can be suppressed.

[0155] A catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of catalyst used may be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture consisting of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature may be 60 to 150°C, and the reaction time may be 3 to 30 hours.

[0156] Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octoate, and zirconium octoate.

[0157] The number average molecular weight (Mn) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and even more preferably 1000 to 5000. If the number average molecular weight is 500 or more, the resin has suitable alkali solubility and is therefore suitable as a resin for photosensitive materials, and if it is 8000 or less, the resin has good coatability and developability.

[0158] In one embodiment, the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 to 7000, preferably 400 to 6000, and more preferably 500 to 5000. When the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 or more, the resin having an epoxy group and a phenolic hydroxyl group can exhibit sufficient alkali solubility. When the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 7000 or less, the strength and heat resistance of the cured coating can be improved. The epoxy equivalent is determined according to JIS K 7236:2009.

[0159] In one embodiment, the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 160 to 500, preferably 170 to 400, and more preferably 180 to 300. If the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 160 or more, the strength and heat resistance of the coating film after curing can be improved. If the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 500 or less, the resin having an epoxy group and a phenolic hydroxyl group can exhibit sufficient alkali solubility. The hydroxyl equivalent is determined according to JIS K 0070:1992.

[0160] In one embodiment, the positive photosensitive resin composition contains 5% to 80% by mass, preferably 10% to 75% by mass, and more preferably 15% to 70% by mass of the second resin (D) based on 100% by mass of the solid content. When the content of the second resin (D) is 5% by mass or more based on 100% by mass of the solid content, dissolution of the exposed area can be promoted, achieving high sensitivity and ensuring the stability and durability of the coating after thermal curing. When the content of the second resin (D) is 80% by mass or less based on 100% by mass of the solid content, the solubility of the unexposed area can be kept low, maintaining a high film residual rate. When the photosensitive resin composition contains two or more types of second resin (D), the above content is the total amount of the second resins.

[0161] <Solubility enhancer (E)> The positive photosensitive resin composition may further contain a dissolution promoter (E) for improving the solubility of the alkali-soluble portion in the developer during development.

[0162] The dissolution promoter (E) may be an organic low molecular weight compound selected from the group consisting of compounds having a carboxy group and compounds having a phenolic hydroxyl group. The dissolution promoter (E) may be used alone or in combination of two or more kinds.

[0163] In the present disclosure, the term "low molecular weight compound" refers to a compound having a molecular weight of not more than 1000. The above organic low molecular weight compound has a carboxy group or multiple phenolic hydroxyl groups and is alkali-soluble.

[0164] Examples of such organic low molecular weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; and aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimellitic acid, and mesitylene acid. aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, and pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umbellic acid; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

[0165] The content of the dissolution promoter (E) in the positive photosensitive resin composition can be 0.1% by mass to 50% by mass, preferably 1% by mass to 35% by mass, and more preferably 2% by mass to 20% by mass, based on 100% by mass of the solid content. If the content of the dissolution promoter (E) is 0.1% by mass or more based on 100% by mass of the solid content, the dissolution of the resin component can be effectively promoted, and if it is 50% by mass or less, excessive dissolution of the resin component can be suppressed, and the pattern formability and surface quality of the coating can be improved.

[0166] <Optional component (F)> The positive photosensitive resin composition may contain, as optional component (F), a heat curing agent, a surfactant, an amine compound, a colorant other than the metal complex dye (C), etc. In the present disclosure, optional component (F) is defined as not falling under any of (A) to (E).

[0167] A thermal radical generator can be used as the thermal curing agent. Preferred examples of the thermal radical generator include organic peroxides, specifically organic peroxides having a 10-hour half-life temperature of 100 to 170°C, such as dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

[0168] The content of the heat curing agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the heat curing agent.

[0169] The positive photosensitive resin composition may contain a surfactant, for example, to improve the coatability, the smoothness of the coating, or the developability of the coating.

[0170] Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafac (registered trademark) F-251, Megafac (registered trademark) F-252, Megafac (registered trademark) F-253, Megafac (registered trademark) F-254, Megafac (registered trademark) F-255, Megafac (registered trademark) F-256, Megafac (registered trademark) F-257, Megafac (registered trademark) F-258, Megafac (registered trademark) F-259 ... Fluorine-based surfactants such as Surflon® S-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-562, and F-563 (all trade names, DIC Corporation), Surflon® S-242, S-243, S-386, S-420, and S-611 (all trade names, AGC Seimi Chemical Co., Ltd.), and organosiloxane polymers KP323, KP326, and KP341 (all trade names, Shin-Etsu Chemical Co., Ltd.). The surfactants can be used alone or in combination of two or more.

[0171] The content of the surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, based on 100 parts by mass of the total solid content excluding the surfactant.

[0172] The positive photosensitive resin composition may contain an amine compound to maintain good storage stability. The amine compound is preferably at least one selected from the group consisting of aliphatic tertiary amines, nitrogen-containing heterocyclic amines, and derivatives of these amines. Examples of aliphatic tertiary amines include triethylamine, tributylamine, trihexylamine, trioctylamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, and N,N-dimethyldodecylamine. Examples of nitrogen-containing heterocyclic amines include N-ethylmorpholine, N-methylmorpholine, N-methylpiperidine, N-methylpyrrolidine, N-ethylpiperidine, N-ethylpyrrolidine, pyridine, 2-methylpyridine, 4-methylpyridine, 2,6-lutidine, N,N-dimethylaminopyridine, diazabicycloundecene, diazabicyclononene, pyrazine, pyrimidine, triazine, and amidine. Examples of the derivatives of these amines include compounds in which any hydrogen atom in the organic group bonded to the nitrogen atom of the amine is substituted with another element or organic group.

[0173] The content of the amine compound is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, based on 100 parts by mass of the total solid content excluding the amine compound.

[0174] [Coating composition] <Solvent (G)> The positive-type photosensitive resin composition can be dissolved in a solvent (G) and used as a coating composition in solution form. For example, a coating composition containing the positive-type photosensitive resin composition can be prepared by dissolving a first resin (A) and an optional second resin (D) in a solvent (G) to obtain a solution, and then mixing the solution with a photoacid generator (B), a metal complex dye (C), and, if necessary, optional components (F) such as a dissolution promoter (E), a heat curing agent, and a surfactant in a predetermined ratio. The viscosity of the coating composition can be adjusted to suit the application method used by changing the amount of solvent (G).

[0175] Examples of the solvent (G) include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol compounds such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Examples of suitable solvents include tate compounds, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and cyclohexanone, esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone, and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination.

[0176] The solid content of the coating composition can be appropriately determined depending on the intended use. For example, the solid content of the coating composition may be 1 to 60 mass %, 3 to 50 mass %, or 5 to 40 mass %.

[0177] The prepared coating composition is usually filtered before use. Examples of filtering methods include a Millipore filter with a pore size of 0.05 to 1.0 μm.

[0178] The coating composition thus prepared also has excellent long-term storage stability.

[0179] [Method of using the positive photosensitive resin composition] When a positive-type photosensitive resin composition is used in radiation lithography, the positive-type photosensitive resin composition is first dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition is applied to a substrate surface, and the solvent is removed by heating or other means to form a coating film. The method for applying the coating composition to the substrate surface is not particularly limited, and for example, spraying, roll coating, slit coating, or spin coating can be used.

[0180] After applying the coating composition to the surface of a substrate, the solvent is usually removed by heating to form a coating (pre-baking). The heating conditions vary depending on the type and blending ratio of each component, but the coating can usually be obtained by heating at 70 to 130°C for 30 seconds to 20 minutes on a hot plate or for 1 to 60 minutes in an oven.

[0181] Next, the prebaked coating is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) through a photomask having a predetermined pattern (exposure step). Preferred radiation is ultraviolet light or visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-ray. In another embodiment, the radiation is ghi-ray.

[0182] After the exposure step, a post-exposure bake (PEB) can be performed to promote decomposition of the acid-decomposable groups by the acid generated from the photoacid generator (B). PEB promotes deprotection of the protected alkali-soluble functional groups in the first resin (A) in the exposed areas, further increasing alkali solubility. Heating conditions vary depending on the types and blending ratios of each component, but PEB can typically be performed at 70 to 140°C, for example, for 30 seconds to 20 minutes on a hot plate or for 1 to 60 minutes in an oven. In one embodiment, PEB after the exposure step can be omitted.

[0183] After the exposure step or PEB step, the coating is developed by contacting it with a developer to remove unnecessary portions and form a pattern in the coating (development step). Examples of the developer include aqueous solutions of alkaline compounds such as inorganic alkaline compounds (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-propylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonane). An aqueous solution containing an appropriate amount of a water-soluble organic solvent (e.g., methanol or ethanol), a surfactant, etc., can also be used as the developer. The development time is typically 30 to 180 seconds. The developing method may be a puddle method, a shower method, or a dipping method. After development, the film is washed with running water for 30 to 90 seconds to remove unnecessary portions, and then air-dried with compressed air or compressed nitrogen, thereby forming a pattern in the film.

[0184] Thereafter, the coating film on which the pattern has been formed can be heat-treated, for example, at 100 to 350°C for 20 to 200 minutes using a heating device such as a hot plate or oven, to obtain a cured coating film (post-baking, heat treatment step). In the heat treatment, the temperature may be maintained constant, or may be increased continuously or stepwise. The heat treatment is preferably carried out in a nitrogen atmosphere.

[0185] The optical density (OD value) of the cured film of the positive photosensitive resin composition is preferably 0.5 or more per 1 μm of film thickness, more preferably 0.7 or more, and even more preferably 1.0 or more. If the OD value of the cured film is 0.5 or more per 1 μm of film thickness, sufficient light-blocking properties can be obtained.

[0186] In one embodiment, a method for producing an organic EL device partition wall or insulating film includes dissolving or dispersing a positive photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a film, removing the solvent contained in the film and drying the film, exposing the dried film to radiation through a photomask, developing the exposed film by contacting it with a developer to form a pattern in the film, and heat-treating the patterned film at a temperature of 100° C. to 350° C. to form an organic EL device partition wall or insulating film. The PEB described above can also be performed after exposure and before development.

[0187] One embodiment is a partition wall for an organic EL device, which comprises a cured product of a positive-type photosensitive resin composition.

[0188] One embodiment is an insulating film for an organic EL device, which comprises a cured product of a positive photosensitive resin composition.

[0189] One embodiment is an organic EL device containing a cured product of the positive photosensitive resin composition. [Example]

[0190] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

[0191] (1) Raw materials The raw materials used in the examples and comparative examples were produced or obtained as follows.

[0192] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the first resin (A) and the second resin (D) were calculated using a calibration curve prepared using a polystyrene standard substance under the following measurement conditions. Device name: Shodex (registered trademark) GPC-101 Column: Shodex (registered trademark) LF-804 Mobile phase: tetrahydrofuran Flow rate: 1.0mL / min Detector: Shodex (registered trademark) RI-71 Temperature: 40℃

[0193] [Production Example 1] Production of a copolymer (PCX-02e) of a polymerizable monomer having an alkali-soluble functional group (phenolic hydroxyl group) and another polymerizable monomer 25.5 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA") and 4.50 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (Daicel Corporation). The two resulting solutions were simultaneously added dropwise over 2 hours to 61.2 g of 1-methoxy-2-propyl acetate (Daicel Corporation) heated to 85 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask, and then reacted at 85 °C for 3 hours. The reaction solution was cooled to room temperature and added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 90°C for 4 hours to recover 32.4g of white powder (PCX-02e). The number average molecular weight of the obtained PCX-02e was 3100 and the weight average molecular weight was 6600.

[0194] [Production Example 2] Production of First Resin (A) (PCX-02e-THF55) in Which Alkali-Soluble Functional Groups (Phenolic Hydroxyl Groups) are Protected with 2-Tetrahydrofuranyl Groups In a 100 mL three-neck flask, 10.00 g of a copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer and 0.60 g of pyridinium salt of p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.) as an acid catalyst were dissolved in 50.00 g of tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.). The mixture was then ice-cooled under a nitrogen gas atmosphere, and 5.51 g of 2,3-dihydrofuran (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. The mixture was then stirred at room temperature for 4 hours. The acid catalyst was neutralized with saturated aqueous sodium bicarbonate, and the aqueous layer was removed. The organic layer was washed twice with water. The tetrahydrofuran was then distilled off. The resulting solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of hexane to precipitate the product. The precipitate was collected by filtration and dried under vacuum at 80 °C for 4 hours, yielding 7.84 g of a white powder. The resulting powder was dissolved in propylene glycol monomethyl ether acetate to obtain a 20% solids solution of the first resin (A) (PCX-02e-THF55) in which the phenolic hydroxyl groups were protected with 2-tetrahydrofuranyl groups. The resulting PCX-02e-THF55 had a number-average molecular weight of 3689, a weight-average molecular weight of 6863, 55 mol% of the phenolic hydroxyl groups protected with acid-decomposable groups, and 44% of the total number of structural units of the first resin (A). The proportion of phenolic hydroxyl groups protected by acid-decomposable groups was calculated using a thermogravimetric differential thermal analyzer (TG / DTA6200, Hitachi High-Tech Science Corporation) from the weight loss rate (%) of the first resin (A) at 260°C when the temperature was increased from room temperature to 250°C at a rate of 10°C / min in a nitrogen gas flow, held for 10 minutes, and then further increased to 400°C at a rate of 10°C / min.

[0195] [Production Example 3] Production of First Resin (A) (PCX-02e-POE48) in Which Alkali-Soluble Functional Groups (Phenolic Hydroxyl Groups) are Protected with 1-n-Propoxyethyl Groups In a 300 mL three-neck flask, 22.00 g of a copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer and 13.16 g of pyridinium salt of p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.) as an acid catalyst were dissolved in 88.00 g of tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.). The mixture was then ice-cooled under a nitrogen gas atmosphere, and 9.93 g of propyl vinyl ether (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. The mixture was then stirred at room temperature for 2.5 hours. The acid catalyst was neutralized with saturated aqueous sodium bicarbonate, and the aqueous layer was removed. The organic layer was further washed twice with water. The tetrahydrofuran was then distilled off. The resulting solid was dissolved in 110.0 g of ethyl acetate and added dropwise to 400 g of hexane to precipitate the product. The precipitate was collected by filtration and dried under vacuum at 80°C for 4 hours, yielding 24.3 g of a white powder. The resulting powder was dissolved in propylene glycol monomethyl ether acetate to obtain a 20% solids solution of the first resin (A) (PCX-02e-POE48) in which the phenolic hydroxyl groups were protected with 1-n-propoxyethyl groups. The resulting PCX-02e-POE48 had a number-average molecular weight of 4,336, a weight-average molecular weight of 7,939, 48 mol% of the phenolic hydroxyl groups protected with acid-decomposable groups, and 41% of the total number of structural units of the first resin (A). The proportion of phenolic hydroxyl groups protected by acid-decomposable groups was calculated using a thermogravimetric differential thermal analyzer (TG / DTA6200, Hitachi High-Tech Science Corporation) from the weight loss rate (%) of the first resin (A) at 260°C when the temperature was increased from room temperature to 250°C at a rate of 10°C / min in a nitrogen gas flow, held for 10 minutes, and then further increased to 400°C at a rate of 10°C / min.

[0196] [Production Example 4] Production of First Resin (A) (PCX-02e-Boc5) in Which Alkali-Soluble Functional Groups (Phenolic Hydroxyl Groups) are Protected with tert-Butoxycarbonyl Groups In a 300 mL three-neck flask, 10.00 g of a copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer and 0.52 g of di-tert-butyl dicarbonate (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.00 g of tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.). Then, under a nitrogen gas atmosphere, 0.0058 g of dimethylaminopyridine (Tokyo Chemical Industry Co., Ltd.) was added as a catalyst. The mixture was then stirred at room temperature for 2.5 hours. The reaction solution was added dropwise to 250 g of hexane to precipitate the product. The precipitate was collected by filtration and vacuum dried at 80 °C for 4 hours to obtain 8.74 g of a white powder. The resulting powder was dissolved in propylene glycol monomethyl ether acetate to obtain a 20% solids solution of the first resin (A) (PCX-02e-Boc5) in which the phenolic hydroxyl groups were protected with tert-butoxycarbonyl groups. The resulting PCX-02e-Boc5 had a number-average molecular weight of 3,814, a weight-average molecular weight of 6,896, a proportion of phenolic hydroxyl groups protected with acid-decomposable groups of 5 mol%, and the number of structural units represented by formula (3) in which at least one phenolic hydroxyl group was protected with an acid-decomposable group of 4% of the total number of structural units of the first resin (A). The proportion of phenolic hydroxyl groups protected with acid-decomposable groups was calculated using a thermogravimetric differential thermal analyzer (TG / DTA6200, Hitachi High-Tech Science Corporation) from the weight loss (%) of the first resin (A) at 260°C when heated from room temperature to 250°C at a rate of 10°C / min in a nitrogen gas flow, held for 10 minutes, and then further heated to 400°C at a rate of 10°C / min.

[0197] As the first resin (A), PCX-02e-THF55 of Production Example 2, PCX-02e-POE48 of Production Example 3, and PCX-02e-Boc5 of Production Example 4 were used.

[0198] The photoacid generator (B) used was a quinone diazide compound, TS-150A (ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinone diazide-5-sulfonic acid), manufactured by Toyo Gosei Co., Ltd.). The structure of TS-150A is shown below. TS-150A has three R groups per molecule, with an average of 1.5 R groups having a quinone diazide structure.

[0199] [ka]

[0200] The photoacid generator (B) used was the oxime-based photoacid generator PAG-103 (2-[2-(propylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, BASF, CAS No. 852246-55-0). PAG-103 generates 1-propanesulfonic acid (pKa = -2.8) upon irradiation with light.

[0201] [Production Example 5] Production of Metal Complex Dye C-1 A commercially available black dye (precursor (1)) specified by the color index of Solvent Black 27 was used as the metal complex dye precursor. 400 g of precursor (1) and 1600 g of γ-butyrolactone (Mitsubishi Chemical Corporation) were added to a 3-liter gallon bottle and heated in an oven at 80°C under an oxygen gas atmosphere for 346 hours to obtain the C8H2O4 in precursor (1). 17 OC3H6NH3 + was partially reacted with γ-butyrolactone to convert it to an amide, thereby producing a γ-butyrolactone solution of metal complex dye C-1 with an ammonium cation content of 16.1 mass %.

[0202] [Production Example 6] Production of Metal Complex Dye C-2 The same precursor (1) as in Production Example 5 was used as the metal complex dye precursor. 800 g of precursor (1) and 3,200 g of γ-butyrolactone (Mitsubishi Chemical Corporation) were added to a 5 L separable flask and stirred at 100° C. for 6 hours under a nitrogen gas atmosphere. 17 OC3H6NH3 + was partially reacted with γ-butyrolactone to convert it to an amide, thereby producing a γ-butyrolactone solution of metal complex dye C-2 with an ammonium cation content of 16.5 mass %.

[0203] [Production Example 7] Production of Metal Complex Dye C-3 The same precursor (1) as in Production Example 5 was used as the metal complex dye precursor. 400 g of precursor (1) and 1600 g of γ-butyrolactone (Mitsubishi Chemical Corporation) were added to a 3-L gallon bottle, and the bottle was then capped and left to stand at room temperature (25°C) for 2 years. 17 OC3H6NH3 + was partially reacted with γ-butyrolactone to convert it to an amide, thereby producing a γ-butyrolactone solution of metal complex dye C-3 with an ammonium cation content of 16.5 mass %.

[0204] As the metal complex dye (C), C-1 to C-4 listed in Table 1 were used. C-4 is the precursor (1) used as the metal complex dye precursor in Production Examples 5 to 7, and this commercially available product was dissolved in γ-butyrolactone at room temperature (25°C) without any processing, and used in the preparation of a positive photosensitive resin composition within 30 minutes after dissolution.

[0205] The ammonium cation content (mass%) of metal complex dyes C-1 to C-4 was determined using the following procedure. 0.5 g of the γ-butyrolactone solution of the metal complex dye was weighed into a 9 mL sample bottle, and a gas chromatography pretreatment reagent was added. The resulting sample was stirred for 1 hour using a mix rotor (VMR-5, AS ONE). Next, 0.1 g of methyl benzoate (Tokyo Chemical Industry Co., Ltd.) and 6.0 g of tetrahydrofuran (Kanto Chemical Co., Ltd.) were added as internal standards and stirred for 10 minutes to prepare a gas chromatography measurement sample. The sample was analyzed using a GC (GC6850 series, Agilent), and the ammonium cation content (mass%) was calculated using a standard internal standard method. The gas chromatography measurement conditions were as follows: Equipment: 6850 series (Agilent) Column: HP-5ms UI (30m x 0.25mm (0.50μm), Agilent) Oven temperature: 100℃ (5 min) → 300℃ (30 min) + 10℃ / min Mobile phase: He Flow rate: 1.0mL / min Detector: FID Split ratio: 1:10 Sample injection volume: 1μL Inlet temperature: 270℃

[0206] [Table 1]

[0207] [Production Example 8] Production of second resin (D) (N695OH70) having epoxy groups and phenolic hydroxyl groups A 300 mL three-neck flask was charged with 2000 g of 1-methoxy-2-propyl acetate (MMPGAC, Daicel Corporation) as a solvent and 500 g of EPICLON® N-695 (DIC Corporation cresol novolac epoxy resin, epoxy equivalent weight 214) as a compound having at least two epoxy groups per molecule, and dissolved under a nitrogen gas atmosphere at 60°C. 235.12 g (0.65 equivalents per epoxy equivalent) of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound and 2.20 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added, and the mixture was reacted at 110°C for 25 hours. The reaction solution was returned to room temperature, diluted with 1-methoxy-2-propyl acetate to a solids content of 20% by mass, and filtered to obtain 2676 g of a solution of second resin (D) (N695OH70) having epoxy groups and phenolic hydroxyl groups. The resulting reaction product had a number average molecular weight of 2419, a weight average molecular weight of 5051, and an epoxy equivalent of 1118.

[0208] As the second resin (D), PCX-02e and N695OH70 were used.

[0209] Phloroglucinol was used as the solubility enhancer (E).

[0210] As optional component (F), a surfactant (leveling agent) Megafac (registered trademark) F-559 (fluorine-based surfactant, DIC Corporation) was used. As additives, trioctylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2-methylpyridine (Fujifilm Wako Pure Chemical Industries, Ltd.) were used.

[0211] As the solvent (G), a mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA=40:60 (mass ratio)) was used.

[0212] (2) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[0213] [Solubility of unexposed areas] A glass substrate (72 mm × 72 mm × 0.7 mm) was bar-coated with a positive-type photosensitive resin composition to a dry film thickness of 2.6 μm. After vacuum drying at room temperature for 60 seconds, the substrate was prebaked by heating on a lidded hot plate at 100°C for 100 seconds. The substrate was then heated on a lidded hot plate at 115°C for 200 seconds for PEB. The dry film thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.), and the substrate was then subjected to alkaline development for 30 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide in a spin development device (AD-1200, Takizawa Sangyo Co., Ltd.). The film thickness after alkaline development was again measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.), and the film thickness (μm) dissolved before and after development was used as an index of the solubility of the unexposed area. Positive photosensitive resin compositions in which the dissolved film thickness was 0.9 μm or less before and after development were judged to have high sensitivity because the unexposed areas had adequate alkali solubility resistance and the film thickness difference between the unexposed and exposed areas was easily generated.

[0214] [Hole diameter] A glass substrate (72 mm × 72 mm × 0.7 mm) was bar-coated with a positive photosensitive resin composition to a dry film thickness of 2.6 μm, and after vacuum drying for 90 seconds, the composition was pre-baked by heating on a hot plate with a lid at 100°C for 100 seconds. The composition was exposed to 150 mJ / cm through a quartz photomask (having a φ10 μm pattern) using an exposure device (product name Multilight ML-251A / B, Ushio Inc.) equipped with an ultra-high pressure mercury lamp. 2The film was exposed to UV light. The exposure dose was measured using an ultraviolet integrating actinometer (product name UIT-150, light-receiving part UVD-S365, Ushio Inc.). After exposure, the film was heated on a lidded hot plate at 115°C for 200 seconds to perform PEB. Subsequently, using a spin developer (AD-1200, Takizawa Sangyo Co., Ltd.), alkaline development was performed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 30 seconds. The film was then cured by heating at 250°C for 60 minutes in an inert oven (DN411I, Yamato Scientific Co., Ltd.). After curing, holes formed in the film were observed using a microscope (VHX-6000, Keyence Corporation), and the hole diameter (μm) obtained was used as an index of sensitivity. Positive photosensitive resin compositions that could be formed without residue and had hole diameters in the range of 6.0 to 11.0 μm were determined to have good pattern formability.

[0215] [OD value of cured film] A positive photosensitive resin composition was spin-coated onto a glass substrate (100 mm × 100 mm × 1 mm) to a dry film thickness of approximately 1.5 μm, and the coating was heated on a hot plate at 120°C for 80 seconds to evaporate the solvent. The coating was then cured at 250°C for 60 minutes in a nitrogen gas atmosphere to obtain a coating. The OD value of the cured coating was measured using a transmission densitometer (BMT-1, Sakata Inx Engineering Co., Ltd.), corrected for the OD value of the glass alone, and converted to an OD value per 1 μm of coating thickness. The coating thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.).

[0216] (3) Preparation and evaluation of positive photosensitive resin compositions [Examples 1 to 4, Comparative Examples 1 and 2] The first resin (A) and the second resin (D) were mixed and dissolved according to the composition shown in Table 2. To the resulting solution, the photoacid generator (B), metal complex dye (C), dissolution promoter (E), optional component (F), and GBL / PGMEA mixed solvent (G) shown in Table 2 were added and further mixed. After visually confirming that the components had dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solids concentration of 12% by mass. The mass % of the composition in Table 2 is a value calculated as the solids content. The evaluation results of the positive photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 2.

[0217] [Table 2] [Industrial Applicability]

[0218] The positive-type photosensitive resin composition according to the present disclosure can be suitably used in radiation lithography for forming partition walls or insulating films of organic EL devices. Organic EL devices having partition walls or insulating films formed from the positive-type photosensitive resin composition according to the present disclosure are suitably used as electronic components for display devices that exhibit good contrast.

Claims

1. A method for producing a positive photosensitive resin composition comprising: a first resin (A) having a plurality of alkali-soluble functional groups, at least a portion of which are protected with acid-decomposable groups; a photoacid generator (B); and a metal complex dye (C) containing an ammonium cation, the method comprising the following steps 1 and 2: The method for producing a positive photosensitive resin composition, wherein the ammonium cation is a compound represented by formula (8): R x R y NH 2 + (8) (In formula (8), R x and R y each independently represent a hydrogen atom or an organic group.) Step 1: A modification step in which a metal complex dye precursor (c) containing an ammonium cation is reacted with a compound having an amine-reactive functional group to reduce the ammonium cation content in the metal complex dye precursor (c) to obtain a metal complex dye (C). Step 2: A mixing step of mixing the first resin (A), the photoacid generator (B), and the metal complex dye (C) obtained in Step 1.

2. 2. The method for producing a positive photosensitive resin composition according to claim 1, wherein the compound having an amine-reactive functional group is at least one selected from the group consisting of ketones and esters.

3. 3. The method for producing a positive photosensitive resin composition according to claim 1, wherein the compound having an amine-reactive functional group is γ-butyrolactone.

4. 4. The method for producing a positive photosensitive resin composition according to claim 1, wherein in the step 1, the metal complex dye precursor (c) is reacted with the compound having an amine-reactive functional group so that the content of ammonium cations in the metal complex dye (C) is 21 mass% or less.

5. The method for producing the positive photosensitive resin composition according to any one of claims 1 to 4, wherein in the step 1, the compound having an amine-reactive functional group is used as a solvent, the metal complex dye precursor (c) is dissolved in the solvent, and the resulting solution is stirred or allowed to stand.

6. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 5, wherein in step 1, the reaction temperature is 0 to 200°C.

7. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 6, wherein in step 1, the reaction time is 0.01 hours or more.

8. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 7, wherein the metal element forming the metal complex ion contained in the metal complex dye precursor (c) is at least one selected from the group consisting of chromium, copper, cobalt, nickel, and iron.

9. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 8, wherein the metal complex dye precursor (c) is at least one black dye defined by the Color Index (C.I.) of Solvent Black 22 to 47.

10. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 9, wherein the first resin (A) has a plurality of phenolic hydroxyl groups, and at least a part of the plurality of phenolic hydroxyl groups is protected by the acid-decomposable group.

11. 11. The method for producing a positive photosensitive resin composition according to claim 10, wherein the first resin (A) is a copolymer of a polymerizable monomer having one or more phenolic hydroxyl groups, at least a part or all of the phenolic hydroxyl groups being protected with the acid-decomposable group, and another polymerizable monomer.

12. The first resin (A) is represented by formula (3): 【Chemistry 1】 (In formula (3), R １ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ５ is the acid-decomposable group, r is an integer of 0 to 5, and s is an integer of 0 to 5, with the proviso that r+s is an integer of 1 to 5. and s is an integer of 1 or more.

13. The first resin (A) is represented by formula (2): 【Chemistry 2】 (In formula (2), R ２ and R ３ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R ４ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The method for producing a positive photosensitive resin composition according to claim 11 or 12, which has a structural unit represented by the following formula:

14. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 13, wherein the positive photosensitive resin composition further comprises a second resin (D), and the second resin (D) is at least one selected from the group consisting of a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group, and a resin having an epoxy group and a phenolic hydroxyl group, and does not have the alkali-soluble functional group protected by the acid-decomposable group.

15. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 14, wherein the positive photosensitive resin composition contains the metal complex dye (C) in an amount of 10% by mass to 60% by mass based on 100% by mass of the solid content.

16. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 15, wherein the positive photosensitive resin composition contains the photoacid generator (B) in an amount of 1% by mass to 50% by mass based on 100% by mass of the solid content.

17. The method for producing a positive photosensitive resin composition according to any one of claims 1 to 16, wherein the optical density (OD value) of a cured coating of the positive photosensitive resin composition is 0.5 or more per 1 µm of film thickness.

18. A positive photosensitive resin composition comprising: a first resin (A) having a plurality of alkali-soluble functional groups, at least a portion of which are protected with acid-decomposable groups; a photoacid generator (B); and a metal complex dye (C) containing ammonium cations, wherein the metal complex dye (C) has an ammonium cation content of 21 mass% or less; The positive photosensitive resin composition, wherein the ammonium cation is a compound represented by formula (8): R x R y NH 2 + (8) (In formula (8), R x and R y each independently represent a hydrogen atom or an organic group.)

19. A partition wall for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to claim 18.

20. An insulating film for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to claim 18.

21. An organic EL device comprising a cured product of the positive photosensitive resin composition according to claim 18.

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