Positive-type photosensitive resin composition and organic EL device partition wall

Abstract

Provided is a high-sensitive photosensitive resin composition which contains a black colorant and by which development and pattern formation are possible even with a low exposure amount. A positive-type photosensitive resin composition according to one embodiment contains: a first resin (A) having a plurality of phenolic hydroxyl groups, at least some of which are protected with an acid-labile group; a second resin (B) having an epoxy group and a phenolic hydroxyl group; at least one colorant (C) selected from the group consisting of a black dye and a black pigment; and a photoacid generator (D).

Description

[Technical field]

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

[0002] In display devices such as organic electroluminescence displays (OLEDs), a partition material is used in the gaps between colored patterns in the display area or in the edges of the peripheral parts of the display area in order to improve display characteristics. In the manufacture of organic electroluminescence display devices, partitions are first formed to prevent organic material pixels from contacting each other, and organic material pixels are formed between the partitions. These partitions are generally formed by photolithography using a photosensitive resin composition and have insulating properties. In detail, a photosensitive resin composition is applied onto a substrate using an application device, and volatile components are removed by heating or other means, and then the substrate is exposed to light through a mask, and then developed by removing the unexposed parts in the case of a negative type and the exposed parts in the case of a positive type with a developer such as an alkaline aqueous solution, and the resulting pattern is heat-treated to form partitions (insulating films). Next, organic materials that emit light of three colors, red, green, and blue, are formed into films between the partitions by an inkjet method or the like to form pixels of the organic electroluminescence display device.

[0003] In recent years, in this field, there has been a demand for higher performance and higher definition of pixels due to the miniaturization of display devices and the diversification of contents to be displayed. In order to increase the contrast in display devices and improve visibility, attempts have been made to impart light-shielding properties to partition materials using colorants. However, when the partition material is given light-shielding properties, the photosensitive resin composition tends to have low sensitivity, which may result in a longer exposure time and a decrease in productivity. Therefore, the photosensitive resin composition used to form the partition material containing a colorant is required to have higher sensitivity.

[0004] Patent Document 1 (JP 2001-281440 A) describes a radiation-sensitive resin composition that exhibits high light-shielding properties through heat treatment after exposure, in which titanium black is added to a positive-type radiation-sensitive resin composition that contains an alkali-soluble resin and a quinone diazide compound.

[0005] 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.

[0006] 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-type radiation-sensitive resin composition that contains an alkali-soluble resin and a quinone diazide compound. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2001-281440 A [Patent Document 2] JP 2002-116536 A [Patent Document 3] JP 2010-237310 A Summary of the Invention [Problem to be solved by the invention]

[0008] In the photosensitive resin composition used for forming a colored partition wall material, a considerable amount of colorant must be used in order to sufficiently increase the light-shielding property of the cured film. When such a large amount of colorant is used, the radiation irradiated to the coating of the photosensitive resin composition is absorbed by the colorant, so that the effective intensity of the radiation in the coating is reduced and the photosensitive resin composition is not sufficiently exposed, resulting in a deterioration in pattern formability.

[0009] In forming a partition wall in an organic EL element, it is important that the material for forming the partition wall has high sensitivity from the viewpoint of productivity, etc. However, when a black photosensitive resin composition containing a colorant is used, exposure failure occurs under normally used exposure conditions, and for example, the exposure time needs to be extended, which is a factor in reducing productivity. Therefore, it is strongly desired to reduce the exposure dose of the photosensitive resin composition to reduce energy costs and increase throughput.

[0010] An object of the present invention is to provide a highly sensitive photosensitive resin composition containing a black colorant, which allows development and pattern formation even at a low exposure dose. [Means for solving the problem]

[0011] The present inventors have discovered that by forming a positive-type photosensitive resin composition into a chemically amplified system that includes a first resin having a plurality of phenolic hydroxyl groups, at least a portion of which is protected with an acid-decomposable group, in combination with a specific second resin having an alkali-soluble functional group, it is possible to achieve development and pattern formation even with a low exposure dose, despite the inclusion of a black colorant.

[0012] That is, the present invention includes the following aspects. [1] a first resin (A) having a plurality of phenolic hydroxyl groups, at least a portion of which is protected with an acid-decomposable group; A second resin (B) having an epoxy group and a phenolic hydroxyl group; At least one colorant (C) selected from the group consisting of black dyes and black pigments; A photoacid generator (D); A positive-type photosensitive resin composition comprising: [2] The positive photosensitive resin composition according to [1], wherein the first resin (A) is an alkaline aqueous solution-soluble copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, the copolymer having a plurality of phenolic hydroxyl groups, at least a portion of which is protected by the acid-decomposable group. [3] The positive photosensitive resin composition according to either [1] or [2], wherein the acid-decomposable group of the first resin (A) is a 1-alkoxyalkyl group. [4] 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 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 the first resin (A) has at least one structural unit represented by the formula: wherein s is an integer of 1 or more. [5] 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 alkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a straight chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 4 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 positive photosensitive resin composition according to any one of [2] to [4], having a structural unit represented by the following formula: [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein 10 mol % to 95 mol % of the phenolic hydroxyl groups of the first resin (A) are protected with the acid-decomposable group. [7] The positive photosensitive resin composition according to any one of [1] to [6], wherein 5 mol % to 65 mol % of phenolic hydroxyl groups of the first resin (A) are protected with the acid-decomposable group, based on the total amount of alkali-soluble functional groups of the first resin (A) and the second resin (B). [8] The positive photosensitive resin composition according to any one of [1] to [7], comprising 20 mass % to 90 mass % of the first resin (A) based on the total mass of the first resin (A) and the second resin (B). [9] The positive photosensitive resin composition according to any one of [1] to [8], comprising 10 parts by mass to 150 parts by mass of the colorant (C) based on a total of 100 parts by mass of the first resin (A) and the second resin (B).

[10] The positive photosensitive resin composition according to any one of [1] to [9], comprising 0.1 to 85 parts by mass of the photoacid generator (D) based on a total of 100 parts by mass of the first resin (A) and the second resin (B).

[11] The positive photosensitive resin composition according to any one of [1] to

[10] , 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.

[12] The second resin (B) is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and is represented by the formula (5): [ka] (In formula (5), 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.) The positive photosensitive resin composition according to any one of [1] to

[11] , wherein the compound has a structure represented by the formula:

[13] The positive photosensitive resin composition according to

[12] , wherein the compound having at least two epoxy groups in one molecule is a novolac type epoxy resin.

[14] The positive photosensitive resin composition according to either

[12] or

[13] , wherein the hydroxybenzoic acid compound is a dihydroxybenzoic acid compound.

[15] The positive photosensitive resin composition according to any one of [1] to

[14] , wherein the second resin (B) has an epoxy equivalent of 300 to 1800, and the photoacid generator (D) generates trifluoromethanesulfonic acid upon irradiation with light.

[16] A partition wall for an organic electroluminescence device, comprising a cured product of the positive photosensitive resin composition according to any one of [1] to

[15] .

[17] An insulating film for an organic electroluminescence device, comprising a cured product of the positive photosensitive resin composition according to any one of [1] to

[15] .

[18] An organic electroluminescence device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to

[15] . Effect of the Invention

[0013] According to the present invention, it is possible to provide a highly sensitive photosensitive resin composition containing a black colorant, which allows development and pattern formation even at a low exposure dose. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention will be described in detail below.

[0015] In the present disclosure, "alkali-soluble" and "alkali aqueous solution soluble" mean that the positive photosensitive resin composition or a component thereof, or a coating or cured coating of the positive photosensitive resin composition, is soluble in an alkaline aqueous solution, for example, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. "Alkali-soluble functional group" means a group that imparts such alkali solubility to the positive photosensitive resin composition or a component thereof, or a coating or cured coating of the positive photosensitive resin composition. Examples of the alkali-soluble functional group include a phenolic hydroxyl group, a carboxy group, a sulfo group, a phosphoric acid group, an acid anhydride group, and a mercapto group.

[0016] 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.

[0017] In this disclosure, a "radically polymerizable functional group" refers to one or more ethylenically unsaturated groups.

[0018] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0019] In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin or polymer refer to values ​​calculated as standard polystyrene, measured by gel permeation chromatography (GPC).

[0020] A positive-type photosensitive resin composition according to one embodiment includes a first resin (A) having a plurality of phenolic hydroxyl groups, at least a portion of which is protected with an acid-decomposable group, a second resin (B) having an epoxy group and a phenolic hydroxyl group, at least one colorant (C) selected from the group consisting of black dyes and black pigments, and a photoacid generator (D).

[0021] In one embodiment, the positive photosensitive resin composition contains 10% by mass to 80% by mass of the first resin (A), preferably 20% by mass to 65% by mass, and more preferably 30% by mass to 50% by mass, based on 100% by mass of the solid content. When the content of the first resin (A) is 10% by mass or more based on 100% by mass of the solid content, a chemical amplification function can be imparted to the photosensitive resin composition, thereby realizing 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 can be reduced, and the solubility of the exposed area can be increased, thereby realizing high sensitivity. In the present disclosure, the "solid content" refers to the total mass of the components including the first resin (A), the second resin (B), the colorant (C), the photoacid generator (D), the dissolution promoter (E), and the optional component (F), excluding the solvent (G).

[0022] In one embodiment, the positive photosensitive resin composition contains 5% by mass to 50% by mass of the second resin (B), preferably 10% by mass to 40% by mass, and more preferably 15% by mass to 30% by mass, based on 100% by mass of the solid content. When the content of the second resin (B) is 5% by mass or more based on 100% by mass of the solid content, it is possible to promote dissolution of the exposed area to achieve high sensitivity, and to ensure the stability and durability of the coating after thermal curing. When the content of the second resin (B) is 50% by mass or less based on 100% by mass of the solid content, it is possible to keep the solubility of the unexposed area low and maintain a high residual film rate.

[0023] In one embodiment, the positive photosensitive resin composition contains 20% by mass to 90% by mass of the first resin (A), preferably 35% by mass to 80% by mass, and more preferably 50% by mass to 75% by mass of the first resin (A) based on the total mass of the first resin (A) and the second resin (B). By making the content of the first resin (A) 20% by mass or more, it is possible to impart a chemical amplification function to the photosensitive resin composition and realize high sensitivity. By making the content of the first resin (A) 90% by mass or less, it is possible to increase the solubility of the exposed area and realize high sensitivity.

[0024] [First resin (A)] The first resin (A) is not particularly limited as long as it has a plurality of phenolic hydroxyl groups, and at least a portion of the plurality of phenolic hydroxyl groups is protected by an acid-decomposable group. The phenolic hydroxyl group is an alkali-soluble functional group, and by protecting a portion of the phenolic hydroxyl group by an acid-decomposable group, the alkali solubility of the first resin (A) before exposure is suppressed. The first resin (A) may have an alkali-soluble functional group other than the phenolic hydroxyl group, and the alkali-soluble functional group may be protected by an acid-decomposable group similarly to the phenolic hydroxyl group. In the presence of an acid generated during exposure, post-exposure bake (PEB, post exposure bake) is performed as necessary to promote decomposition (deprotection) of the acid-decomposable group, and the phenolic hydroxyl group is regenerated. This promotes the alkali dissolution of the first resin (A) in the exposed area during development. The first resin (A) may have an alkali-soluble functional group other than the phenolic hydroxyl group, such as a carboxy group, a sulfo group, a phosphoric acid group, an acid anhydride group, a mercapto group, etc. The first resin (A) may be used alone or in combination of two or more kinds. For example, the first resin (A) may be a combination of two or more kinds of resins that differ in polymer structural units, acid-decomposable groups, protection rates of phenolic hydroxyl groups, or combinations thereof.

[0025] Protection of phenolic hydroxyl groups with acid-labile groups The first resin (A) can be obtained by protecting some of the phenolic hydroxyl groups of the base resin (a) having a plurality of phenolic hydroxyl groups with an acid-decomposable group. The first resin (A) having phenolic hydroxyl groups protected with an acid-decomposable group has a partial structure of Ar-OR, where Ar represents an aromatic ring derived from phenol and R represents an acid-decomposable group.

[0026] 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 of the acid-decomposable group include groups having a tertiary alkyl group, such as 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, and a 1,1-dimethyl-propoxycarbonyl group; silyl groups, such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group, and a t-butyldiphenylsilyl group; and groups represented by the formula (7): -CR 6 R 7 -OR 8 (7) (In formula (7), R 6 and R 7 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; R 8 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; R 6 or R 7 One of the two and R 8 may be bonded to form a ring structure. The group represented by formula (7) forms an acetal structure or a ketal structure together with the oxygen atom derived from the phenolic hydroxyl group. These acid-decomposable groups may be used alone or in combination of two or more. The number of ring members in the ring structure is preferably 3 to 10. 6 , R 7 and R 8 may be substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

[0027] Since a positive-type photosensitive resin composition having high sensitivity can be obtained even with a low exposure dose, the acid-decomposable group is preferably a group represented by formula (7). 6 and R 7More preferably, R is each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. 8 R is more preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. 8 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 (7), in which R 6 or R 7 One of the two and R 8 In this case, R which is not involved in the formation of the ring structure may be preferably used. 6 or R 7 is preferably a hydrogen atom. The number of ring members in the ring structure is preferably 3 to 10. Examples of such an acid-decomposable group include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with the 2-tetrahydrofuranyl group being preferred.

[0028] The protection reaction of the phenolic hydroxyl group can be carried out under known conditions using a general protecting agent. For example, the base resin (a) of the first resin (A) is reacted with the protecting agent in the presence of an acid or base at a reaction temperature of -20 to 50°C without a solvent or in a solvent such as toluene or hexane to obtain the first resin (A).

[0029] As the protecting agent, a known protecting agent capable of protecting a phenolic hydroxyl group 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 triethyl 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.

[0030] Examples of the acid 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 the base include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium hydrogencarbonate, 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.

[0031] In another embodiment, the first resin (A) can be obtained by protecting the phenolic hydroxyl group of a polymerizable monomer having a phenolic hydroxyl group with an acid-decomposable group, and then polymerizing or copolymerizing the polymerizable monomer having the phenolic hydroxyl group protected with the acid-decomposable group and, if necessary, other polymerizable monomers. The protection of the phenolic hydroxyl group of the polymerizable monomer having a phenolic hydroxyl group can be performed in the same manner as the protection of the phenolic hydroxyl group of the base resin (a).

[0032] <Base resin (a)> Examples of the base resin (a) of the first resin (A) include polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamic acid resin, polybenzoxazole resin, polybenzoxazole resin precursor, silicone resin, cyclic olefin polymer, cardo resin, and derivatives of these resins, each of which has a plurality of phenolic hydroxyl groups. For example, a derivative of a phenolic resin may be a polyalkenylphenolic resin in which an alkenyl group is bonded to a benzene ring, and a derivative of a polystyrene resin may be a hydroxypolystyrene resin in which a phenolic hydroxyl group and a hydroxyalkyl group or an alkoxy group are bonded to a benzene ring. As the base resin (a), a homopolymer or copolymer of a polymerizable monomer having a phenolic hydroxyl group may also be used. These base resins (a) may be used alone or in combination of two or more kinds. The base resin (a) may have a radical polymerizable functional group. In one embodiment, the base resin (a) has a (meth)acryloyloxy group, an allyl group, or a methallyl group as a radical polymerizable functional group.

[0033] <Alkaline Aqueous Solution Soluble Copolymer (a1) of Polymerizable Monomer Having a Phenolic Hydroxyl Group and Other Polymerizable Monomer> In one embodiment, the base resin (a) of the first resin (A) is an aqueous alkali solution soluble copolymer (a1) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, and the aqueous alkali solution soluble copolymer (a1) has a plurality of phenolic hydroxyl groups. In this embodiment, the first resin (A) is an aqueous alkali solution soluble copolymer (a1) in which at least a portion of the plurality of phenolic hydroxyl groups is protected with an acid decomposable group. The aqueous alkali solution soluble copolymer (a1) may further have an alkaline soluble functional group other than the phenolic hydroxyl group, such as a carboxy group, a sulfo group, a phosphoric acid group, an acid anhydride group, or a mercapto group. The polymerizable functional group possessed by the polymerizable monomer may be a radical polymerizable functional group, for example, CH 2 =CH-, CH2 =C(CH 3 )-, CH 2 =CHCO-, CH 2 =C(CH 3 )CO-, -OC-CH=CH-CO-, etc.

[0034] The aqueous alkali solution soluble copolymer (a1) can be produced, for example, by radical polymerization of a polymerizable monomer having a phenolic hydroxyl group and other polymerizable monomers. After synthesizing the copolymer by radical polymerization, the phenolic hydroxyl group may be added to the copolymer. Examples of the polymerizable monomer having a phenolic hydroxyl group include 4-hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, and 4-hydroxyphenyl maleimide. Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, ether compounds of vinyl alcohol such as acrylamide, acrylonitrile, and vinyl-n-butyl ether, alkyl (meth)acrylates, 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 isobol. Examples of the acrylic acid ester include (meth)acrylic acid esters such as nyl(meth)acrylate, N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide, maleic anhydride, maleic acid monoesters, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, β-styryl(meth)acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid. From the viewpoint of heat resistance, etc., it is preferable that the aqueous alkali solution-soluble copolymer (a1) has one or more cyclic structures such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure.

[0035] As a polymerizable monomer having a phenolic hydroxyl group, the following formula (1) [ka] In the 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. 1 is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, and more preferably 1. As such a polymerizable monomer having a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferable.

[0036] As other polymerizable monomers, there may be mentioned a monomer represented by the formula (2): [ka] In the 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 alkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 R is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 4 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. 2 and R 3 R is preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 4 is preferably a cyclic alkyl group having 4 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 4 to 12 carbon atoms, or a phenyl group. As such other polymerizable monomers, phenylmaleimide and cyclohexylmaleimide are particularly preferred.

[0037] In one embodiment, the aqueous alkali solution soluble copolymer (a1) is represented by 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 alkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a straight chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 4 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:

[0038] It is particularly preferable to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having a phenolic hydroxyl group and phenylmaleimide or cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radical polymerization of these polymerizable monomers, it is possible to improve shape retention and developability and also reduce outgassing.

[0039] The polymerization initiator used in producing the base resin (a) or the aqueous alkali solution-soluble copolymer (a1) by radical polymerization may be, but is 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-2,2'-azobis(2,4-dimethylvaleronitrile); Peroxide polymerization initiators having a 10-hour half-life temperature of 100 to 170°C, such as 1,5-di(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. The amount of the polymerization initiator used is preferably generally 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, and 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable monomers.

[0040] A RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. The RAFT agent may be, but is not limited to, a thiocarbonylthio compound such as a dithioester, a dithiocarbamate, a trithiocarbonate, or a xanthate. The RAFT agent may be used in an amount of 0.005 to 20 parts by mass, and preferably in an amount of 0.01 to 10 parts by mass, relative to 100 parts by mass of the total amount of polymerizable monomers.

[0041] The weight average molecular weight (Mw) of the base resin (a) or the aqueous alkali solution soluble copolymer (a1) can be 3000 to 80000, preferably 4000 to 70000, and more preferably 5000 to 60000. The number average molecular weight (Mn) can be 1000 to 30000, preferably 1500 to 25000, and more preferably 2000 to 20000. 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, number average molecular weight, and polydispersity in the above ranges, a positive photosensitive resin composition having excellent alkali solubility and developability can be obtained.

[0042] In one embodiment, 10 mol% to 95 mol%, preferably 20 mol% to 80 mol%, more preferably 25 mol% to 70 mol% of the phenolic hydroxyl groups of the first resin (A) are protected with an acid decomposable group. In the first resin (A), by setting the ratio of the phenolic hydroxyl groups protected with an acid decomposable group to 10 mol% or more, a chemical amplification function can be imparted to the photosensitive resin composition, thereby realizing high sensitivity. By setting the ratio of the phenolic hydroxyl groups protected with an acid decomposable group to 95 mol% or less, the amount of the remaining acid decomposable groups that do not react during exposure can be reduced, and the solubility of the exposed area can be increased, thereby realizing high sensitivity. The ratio of the phenolic hydroxyl groups protected with an acid decomposable group is calculated from the weight loss rate (%) of the first resin (A) measured by a thermogravimetric differential thermal analyzer (TG / DTA). In the present disclosure, when the first resin (A) is a combination of two or more resins with different protection rates, the protection rate of the phenolic hydroxyl groups 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.

[0043] In one embodiment, in the positive photosensitive resin composition, 5 mol % to 65 mol %, preferably 10 mol % to 55 mol %, more preferably 15 mol % to 50 mol % of the phenolic hydroxyl groups of the first resin (A) are protected with an acid-decomposable group based on the total of the alkali-soluble functional groups of the first resin (A) and the second resin (B). By setting the protection rate of the phenolic hydroxyl groups of the first resin (A) to 5 mol % or more based on the total of the alkali-soluble functional groups of the first resin (A) and the second resin (B), a chemical amplification function can be imparted to the photosensitive resin composition to achieve high sensitivity. By setting the protection rate of the phenolic hydroxyl groups of the first resin (A) to 65 mol % or less based on the total of the alkali-soluble functional groups of the first resin (A) and the second resin (B), the solubility of the exposed area can be ensured. The alkali-soluble functional groups that serve as the standard include any carboxy group, sulfo group, phosphoric acid group, acid anhydride group, mercapto group, etc. in addition to the phenolic hydroxyl group.

[0044] In one embodiment, the first resin (A) is an aqueous alkali-soluble copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, the copolymer having a plurality of phenolic hydroxyl groups, at least some of which are protected by acid-decomposable groups. That is, the first resin (A) has an aqueous alkali-soluble copolymer (a1) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer as the base resin (a), and the aqueous alkali-soluble copolymer (a1) has a plurality of phenolic hydroxyl groups, at least some of which are protected by acid-decomposable groups.

[0045] In an embodiment in which the base resin (a) is an aqueous alkali solution-soluble copolymer (a1), the first resin (A) is a copolymer 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 5is 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.) and it is preferable that the first resin (A) has at least one of the above structural units in which s is an integer of 1 or more. 5 The acid-decomposable group is represented by the formula (7): -CR 6 R 7 -OR 8 (7) In formula (7), R 6 and R 7 More preferably, R is each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. 8 is a linear, branched or cyclic alkyl group having 1 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 It is more preferable that R is bonded to form a ring structure having 3 to 10 ring members. 6 , R 7 and R 8 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. 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 the 2-tetrahydrofuranyl group being preferred.

[0046] In an embodiment in which the base resin (a) is an aqueous alkali solution-soluble copolymer (a1), the first resin (A) is a copolymer 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 alkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a straight chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 4 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. 2 and R 3 R is preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 4 is preferably a cyclic alkyl group having 4 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.

[0047] In one embodiment, the number of structural units represented by formula (3) where s is an integer of 1 or more, i.e., structural units represented by formula (3) in which at least one phenolic hydroxyl group is protected by an acid-decomposable group, is 5% to 95%, preferably 15% to 70%, more preferably 25% to 60% of the total number of structural units of the first resin (A). By making the ratio of the above structural units 10% or more, it is possible to impart a chemical amplification function to the photosensitive resin composition and achieve high sensitivity. By making the ratio of the above structural units 95% or less, it is possible to reduce the amount of remaining unreacted acid-decomposable groups, increase the solubility of the exposed area, and achieve high sensitivity.

[0048] [Second resin (B) having an epoxy group and a phenolic hydroxyl group] The second resin (B) having an epoxy group and a phenolic hydroxyl group is an alkaline aqueous solution soluble resin. The second resin (B) may have an alkali-soluble functional group other than the phenolic hydroxyl group. The phenolic hydroxyl group and other alkali-soluble functional groups may be protected with an acid-decomposable group. The second resin (B) can be obtained, for example, by reacting a part of the epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter, sometimes referred to as "epoxy compound") with a carboxy group of a hydroxybenzoic acid compound. The epoxy group of the second resin (B) forms a crosslink by reacting with the phenolic hydroxyl group 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 second resin (B) also functions as a dissolution promoter for the first resin (A) in which the acid-decomposable group is not sufficiently decomposed (deprotected) in the exposed area when exposed to a low exposure dose, and since the phenolic hydroxyl group has a relatively low alkali solubility compared to the carboxyl group, the second resin (B) does not dissolve excessively in the alkaline aqueous solution in the unexposed area. Therefore, by using the second resin (B), the photosensitive resin composition can be made highly sensitive and a high-resolution pattern can be formed. In addition, in the second resin (B), the phenolic hydroxyl group, which has a relatively low acidity as an alkali-soluble functional group, coexists with an epoxy group having reactivity to acid, so that ring-opening polymerization of the epoxy group of the second resin (B) is less likely to proceed compared to a resin having a functional group with a high acidity such as a carboxyl group and an epoxy group. This allows the performance of the photosensitive resin composition, such as alkali solubility and crosslinking reactivity, to be stably maintained for a long period of time.

[0049] Comparing the second resin (B) having both epoxy groups and phenolic hydroxyl groups with a blend of a resin having an epoxy group and a resin having a phenolic hydroxyl group, the resin having an epoxy group in the blend does not have alkali solubility, so that the alkali solubility of the exposed area may decrease. On the other hand, all of the components of the second resin (B) are compounds having alkali soluble functional groups. Therefore, by using the second resin (B), it is possible to easily adjust the alkali solubility of the photosensitive resin composition, and it is possible to impart excellent pattern formability to the photosensitive resin composition.

[0050] The following reaction formula 1 shows an example of a reaction in which one of the epoxy groups of an epoxy compound reacts with a carboxy group of a hydroxybenzoic acid compound to produce a compound having a phenolic hydroxyl group. [ka]

[0051] Examples of compounds having at least two epoxy groups in one 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 only need to have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. Since these compounds are thermosetting, it is common knowledge for those skilled in the art that their structures cannot be unequivocally described due to differences in the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, and the like. An example of the structure of a novolac epoxy resin is shown in formula (4). In formula (4), for example, R 9 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a hydroxyl group, and m is an integer of 1 to 50. [ka]

[0052] Examples of phenol novolac type epoxy resins include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation) and jER (registered trademark)-152 (manufactured by Mitsubishi Chemical Corporation). Examples of cresol novolac type epoxy resins include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) and EOCN (registered trademark)-102S (manufactured by Nippon Kayaku Co., Ltd.). Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), and YD-128 (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F type epoxy resins such as jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corporation) and YDF-170 (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.). Examples of biphenol-type epoxy resins include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, manufactured by DIC Corporation). Examples of alicyclic epoxy resins include EHPE (registered trademark)-3150 (manufactured by Daicel Chemical Industries, Ltd.). Examples of heterocyclic epoxy resins include TEPIC (registered trademark), TEPIC-L, TEPIC-H, and TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.).

[0053] The compound having at least two epoxy groups in one 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 second resin (B) derived from a novolac epoxy resin has excellent pattern formability, easy adjustment of alkali solubility, and little outgassing.

[0054] The hydroxybenzoic acid compound is a compound in which at least one of the 2-6 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, and the like. In terms of enhancing alkaline developability, dihydroxybenzoic acid compounds are preferred. The hydroxybenzoic acid compounds can be used alone or in combination of two or more kinds.

[0055] In one embodiment, the second resin (B) is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and is represented by the formula (5): [ka] In formula (5), 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.

[0056] In the method of obtaining the second resin (B) 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 it is 1.0 equivalents or less, an increase in molecular weight due to a side reaction can be suppressed.

[0057] A catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of the 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. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate.

[0058] The number average molecular weight (Mn) of the second resin (B) is preferably 500 to 8000, more preferably 800 to 6000, and further 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 coating property and developability are good.

[0059] In one embodiment, the epoxy equivalent of the second resin (B) is 300 to 7000, preferably 400 to 6000, and more preferably 500 to 5000. If the epoxy equivalent of the second resin (B) is 300 or more, the second resin (B) can exhibit sufficient alkali solubility. If the epoxy equivalent of the second resin (B) is 7000 or less, the strength and heat resistance of the coating film after curing can be increased. The epoxy equivalent is determined according to JIS K 7236:2009.

[0060] In one embodiment, the hydroxyl equivalent of the second resin (B) is 160 to 500, preferably 170 to 400, and more preferably 180 to 300. If the hydroxyl equivalent of the second resin (B) is 160 or more, the strength and heat resistance of the coating film after curing can be increased. If the hydroxyl equivalent of the second resin (B) is 500 or less, sufficient alkali solubility can be exhibited in the second resin (B). The hydroxyl equivalent is determined according to JIS K 0070:1992.

[0061] In one embodiment, the molar ratio of epoxy groups / phenolic hydroxyl groups in the second resin (B) is 1 / 18 to 9 / 2, preferably 2 / 16 to 8 / 4, and more preferably 3 / 14 to 7 / 6. If the molar ratio of epoxy groups / phenolic hydroxyl groups in the second resin (B) is 1 / 18 or more, the strength and heat resistance of the coating film after curing can be increased. If the molar ratio of epoxy groups / phenolic hydroxyl groups in the second resin (B) is 9 / 2 or less, sufficient alkali solubility can be expressed in the second resin (B). The molar ratio of epoxy groups / phenolic hydroxyl groups is determined based on the theoretical equivalent calculated from the charge ratio of raw materials during the production of the second resin (B), for example, the charge ratio of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound.

[0062] Colorant (C) The colorant (C) is at least one selected from the group consisting of black dyes and black pigments. A black dye and a black pigment may be used in combination. For example, a positive photosensitive resin composition containing the colorant (C) is used to form a black partition wall in an organic EL element, thereby improving the visibility of a display device such as an organic EL display.

[0063] In one embodiment, the colorant (C) includes a black dye. As the black dye, a dye defined by the color index (CI) of Solvent Black 27 to 47 can be used. The black dye is preferably defined by the CI of Solvent Black 27, 29, or 34. When at least one of the dyes defined by the CI of Solvent Black 27 to 47 is used as the black dye, the light-shielding property of the coating of the positive photosensitive resin composition after baking can be maintained. Compared with a positive photosensitive resin composition containing a black dye, a positive photosensitive resin composition containing a black dye has less residue of the colorant (C) during development, and can form a high-definition pattern in the coating.

[0064] A black pigment may be used as the colorant (C). Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigments, and lactam pigments. Surface-treated black pigments may also be used. Examples of commercially available perylene pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF. Examples of commercially available lactam pigments include Irgaphor (registered trademark) Black S0100CF manufactured by BASF. Since the black pigment has high light-shielding properties, it is preferable that the black pigment is at least one selected from the group consisting of carbon black, titanium black, perylene pigments, and lactam pigments.

[0065] In one embodiment, the positive photosensitive resin composition contains 10 to 150 parts by mass of colorant (C) based on 100 parts by mass of the total of the first resin (A) and the second resin (B). When the content of colorant (C) is 10 parts by mass or more based on the total of 100 parts by mass, the light-shielding property of the coating film after baking can be maintained. When the content of colorant (C) is 150 parts by mass or less based on the total of 100 parts by mass, the coating film can be colored without impairing the alkaline developability.

[0066] [Photoacid generator (D)] The positive-type photosensitive resin composition contains a photoacid generator (D). The photoacid generator (D) is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, gamma rays, and electron beams. The photoacid generator (D) promotes decomposition of the acid-decomposable group of the first resin (A) to regenerate the phenolic hydroxyl group, thereby increasing the alkali solubility of the first resin (A). In addition, the presence of the acid generated from the photoacid generator (D) in the portion irradiated with radiation makes the resin in that portion more easily dissolve in an alkaline aqueous solution together with the acid. As a result, a pattern with high sensitivity and high resolution can be formed even with a low exposure dose. The photoacid generator (D) can be used alone or in combination of two or more types.

[0067] The photoacid generator (D) is preferably one that generates an acid having a pKa of 4 or less upon irradiation with radiation, and more preferably one that generates an acid having a pKa of 3 or less. Such a photoacid generator (D) can generate an acid capable of decomposing an acid-decomposable group.

[0068] The photoacid generator (D) is preferably one that generates an acid with a pKa of -15 or more upon irradiation with radiation, and more preferably one that generates an acid with a pKa of -5 or more. Such a photoacid generator (D) can maintain the alkali solubility of the second resin (B) during development without excessively promoting ring-opening polymerization of the epoxy groups of the second resin (B) during exposure and post-exposure bake (PEB).

[0069] Examples of the photoacid generator (D) 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, it is preferable to use oxime sulfonate compounds because of their high sensitivity and high insulating properties.

[0070] An example of the oxime sulfonate compound is a compound represented by the formula (6). [ka]

[0071] In formula (6), R 10 is a substituted or unsubstituted alkyl group, alkoxy group, aryl group, or halogen atom; R 11 and R 12 R is 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. 11 and R 12 may be bonded to form a ring structure. The ring structure preferably has 3 to 10 ring members.

[0072] R 10 The substituted or unsubstituted alkyl group of R includes, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, or an n-propyl group. 10 The substituted or unsubstituted alkoxy group of R includes, for example, a linear or branched alkoxy group having 1 to 5 carbon atoms, and is preferably a methoxy group or an ethoxy group. 10 Examples of the substituents of the alkyl group and alkoxy group in R 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. 10 The alkyl group substituted by R is preferably a fluoroalkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group, and even more preferably a trifluoromethyl group. 10 The substituted or unsubstituted aryl group of R is, 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. 10 Examples of the substituent of 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). 10 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0073] R 11 and R 12 The substituted or unsubstituted aryl group of R is, for example, an aryl group having 6 to 20 carbon atoms, and is preferably a phenyl group or a naphthyl group. 11 and R 12Examples 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. 11 and R 12 Examples of the substituents of the aryl group and heterocyclic group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, and halogen atoms (fluorine atom, chlorine atom, bromine atom, and iodine atom). 11 and R 12 Examples of the acyloxy group include an acetoxy group and a benzoyl group. 11 and R 12 Examples of the alkoxycarbonyl group include an ethoxycarbonyl group. 11 and R 12 Examples of the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. 11 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. 12 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.

[0074] R 11 and R 12 Examples of the oxime sulfonate compound having a ring structure formed by bonding with the above include oxime sulfonate compounds represented by formula (6a). [ka]

[0075] In formula (6a), R 10 is as explained for equation (6), and R 13 are each independently an alkyl group, an alkoxy group, or a halogen atom, and m is an integer of 0 to 5.

[0076] R 13 Examples of the alkyl group in R include linear or branched alkyl groups having 1 to 10 carbon atoms, and are preferably a methyl group, an ethyl group, or an n-propyl group. 13 Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 5 carbon atoms, and are preferably methoxy or ethoxy groups. 13 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 preferable. m is preferably 0 or 1.

[0077] Examples of the oxime sulfonate compound 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.

[0078] In one embodiment, the positive photosensitive resin composition contains 0.5 to 75 parts by mass, preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass of a photoacid generator (D) based on 100 parts by mass of the total of the first resin (A) and the second resin (B). When the content of the photoacid generator (D) is 0.5 parts by mass or more based on the total of 100 parts by mass, high sensitivity can be achieved. When the content of the photoacid generator (D) is 75 parts by mass or less based on the total of 100 parts by mass, alkaline developability is good.

[0079] [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. Examples of the dissolution promoter (E) include organic low molecular weight compounds 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.

[0080] 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.

[0081] 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 camphoric acid; 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.

[0082] The content of the dissolution promoter (E) in the positive photosensitive resin composition can be 0.1 to 50 parts by mass, preferably 1 to 35 parts by mass, and more preferably 2 to 20 parts by mass, based on 100 parts by mass of the total of the first resin (A) and the second resin (B). If the content of the dissolution promoter (E) is 0.1 parts by mass or more based on the total of 100 parts by mass, the dissolution of the resin components can be effectively promoted, and if it is 50 parts by mass or less, excessive dissolution of the resin components can be suppressed, and the pattern formability and surface quality of the coating can be improved.

[0083] [Optional component (F)] The positive photosensitive resin composition may contain, as an optional component (F), a resin other than the first resin (A) and the second resin (B), a heat curing agent, a surfactant, a colorant other than (C), a quinone diazide compound, etc. In the present disclosure, the optional component (F) is defined as not falling under any of (A) to (E).

[0084] Examples of resins other than the first resin (A) and the second resin (B) 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. These resins may or may not have an alkali-soluble functional group.

[0085] A thermal radical generator can be used as the thermal curing agent. A preferred thermal radical generator is an organic peroxide, specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, or other organic peroxides having a 10-hour half-life temperature of 100 to 170°C.

[0086] The content of the heat curing agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the heat curing agent.

[0087] 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. Examples of the surfactant 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; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and nonionic surfactants such as Megafac (registered trademark) F-2. Fluorine-based surfactants such as Surflon (registered trademark) S-242, S-243, S-386, S-420, and S-611 (all trade names, manufactured by ACG Seimi Chemical Co., Ltd.); organosiloxane polymers KP323, KP326, and KP341 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactants can be used alone or in combination of two or more kinds.

[0088] 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.

[0089] The positive photosensitive resin composition may contain a second colorant other than the colorant (C). The second colorant may be a dye, an organic pigment, an inorganic pigment, or the like, and may be used according to the purpose. The second colorant may be used in an amount that does not impair the effect of the present disclosure.

[0090] Examples of dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

[0091] Examples of pigments include CI Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15:1, 15:4, 22, 60, 64, CI Pigment Green 7, and CI Pigment Brown 23, 25, and 26.

[0092] The photoacid generator (D) may be used in combination with a quinone diazide compound. Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via ester, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via sulfonamide, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via ester or sulfonamide. From the viewpoint of contrast between exposed and unexposed areas, it is preferable that 20 mol % or more of the functional groups of the polyhydroxy compound or polyamino compound are substituted with quinone diazide.

[0093] The 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, and 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, TML -BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all trade names, manufactured by 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, manufactured by Asahi Organic Chemical Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and the like, but are not limited thereto.

[0094] Examples of the polyamino compound include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0095] The polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

[0096] 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.

[0097] When a quinone diazide compound is irradiated with ultraviolet light or the like, it generates a carboxy group via the reaction shown in the following reaction formula 2. The generation of a carboxy group makes the exposed portion (coating) soluble in an alkaline aqueous solution, and this portion becomes alkaline developable.

[0098] [ka]

[0099] In one embodiment, the positive photosensitive resin composition contains 0.5 to 75 parts by mass of a quinone diazide compound, preferably 2 to 40 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the total of the first resin (A) and the second resin (B). When the content of the quinone diazide compound is 0.5 parts by mass or more based on the total of 100 parts by mass, high sensitivity can be achieved. When the content of the quinone diazide compound is 75 parts by mass or less based on the total of 100 parts by mass, alkaline developability is good.

[0100] [Solvent (G)] The positive photosensitive resin composition can be used in a solution state by dissolving it in a solvent (G) (however, when a black pigment is contained, the pigment is in a dispersed state). For example, a positive photosensitive resin composition in a solution state can be prepared by mixing a colorant (C), a photoacid generator (D), and, if necessary, an optional component (F) such as a dissolution promoter (E), a thermosetting agent, or a surfactant in a predetermined ratio with a solution obtained by dissolving the first resin (A) and the second resin (B) in a solvent (G). The viscosity of the positive photosensitive resin composition can be adjusted to a value suitable for the coating method to be used by changing the amount of the solvent (G).

[0101] 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; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; Examples of the solvent include ester 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, 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 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. The solvents can be used alone or in combination of two or more.

[0102] The positive photosensitive resin composition can be prepared by dissolving or dispersing the first resin (A), the second resin (B), the colorant (C), and the photoacid generator (D), and optionally the dissolution promoter (E) or the optional component (F) in a solvent (G) and mixing them. The solid content concentration of the positive photosensitive resin composition can be appropriately determined depending on the purpose of use. For example, the solid content concentration of the positive photosensitive resin composition may be 1 to 60 mass%, 3 to 50 mass%, or 5 to 40 mass%.

[0103] When a pigment is used, a known method can be used for dispersing and mixing. For example, ball-type mills such as ball mills, sand mills, bead mills, paint shakers, and rocking mills, blade-type mills such as kneaders, paddle mixers, planetary mixers, and Henschel mixers, and roll-type mills such as three-roll mixers, as well as Raikai mixers, colloid mills, ultrasonics, homogenizers, and rotation-revolution mixers may be used. From the viewpoint of dispersion efficiency and fine dispersion, it is preferable to use a bead mill.

[0104] The prepared positive photosensitive resin composition is usually filtered before use, for example, using a Millipore filter having a pore size of 0.05 to 1.0 μm.

[0105] The positive photosensitive resin composition thus prepared also has excellent long-term storage stability.

[0106] [Method of using the positive-type photosensitive resin composition] When a positive-type photosensitive resin composition is used for radiation lithography, first, the positive-type photosensitive resin composition is 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 of applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method, or the like can be used.

[0107] After the coating composition is applied to the surface of the substrate, the solvent is usually removed by heating to form a coating (pre-baking). The heating conditions vary depending on the types and blending ratios 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 1 to 60 minutes in an oven.

[0108] Next, the prebaked coating is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, synchrotron radiation, etc.) through a photomask having a predetermined pattern (exposure step). When an oxime sulfonate compound is used as the photoacid generator (D), the preferred radiation is ultraviolet light or visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-rays. In another embodiment, the radiation is ghi-rays.

[0109] After the exposure step, a heat treatment (PEB) can be performed to promote decomposition of the acid-decomposable group by the acid generated from the photoacid generator (D). The alkali solubility of the first resin (A) in the exposed area can be increased by PEB. The heating conditions vary depending on the type and blending ratio of each component, but PEB can usually be performed by heating 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.

[0110] After the PEB process, the coating is developed by contacting it with a developer, and unnecessary portions are removed to form a pattern in the coating (development process). As the developer, for example, an aqueous solution of an alkaline compound such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, and the like to an aqueous alkali solution can also be used as the developer. The development time is usually 30 to 180 seconds. The developing method may be any of a puddle method, a shower method, a dipping method, etc. After development, washing with running water is carried out for 30 to 90 seconds to remove unnecessary parts, and the coating is air-dried with compressed air or compressed nitrogen, whereby a pattern can be formed in the coating.

[0111] 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 kept constant, or may be increased continuously or stepwise. The heat treatment is preferably carried out in a nitrogen atmosphere.

[0112] 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.

[0113] In one embodiment, a method for producing an organic EL element partition or insulating film includes dissolving or dispersing a positive-type photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a coating film, removing the solvent contained in the coating and drying the coating, exposing the coating to radiation through a photomask to the dried coating, heating the exposed coating to decompose at least a part of the acid-decomposable groups of the first resin (A), developing the exposed and heated coating by contacting it with a developer to form a pattern in the coating, and heat-treating the coating with the pattern formed thereon at a temperature of 100° C. to 350° C. to form an organic EL element partition or insulating film.

[0114] In one embodiment of the positive photosensitive resin composition, the epoxy equivalent of the second resin (B) having an epoxy group and a phenolic hydroxyl group is 300 to 1800, and the photoacid generator (D) generates trifluoromethanesulfonic acid. If the epoxy equivalent of the second resin (B) is 300 or more and 1800 or less, the heat sagging of the coating during heat treatment can be suppressed. The epoxy equivalent of the second resin (B) having an epoxy group and a phenolic hydroxyl group is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more. The epoxy equivalent of the second resin (B) having an epoxy group and a phenolic hydroxyl group is preferably 1500 or less, more preferably 1000 or less, and even more preferably 900 or less. By using a photoacid generator (D) that generates trifluoromethanesulfonic acid (pKa = -13), which is a super acid, the pattern formability can be improved. The positive photosensitive resin composition of this embodiment is particularly suitable for forming a thick film because of its high sensitivity, and even if the film is exposed to high temperatures during post-baking, the film can be cured while maintaining the pattern shape of the film with high precision, so that the positive photosensitive resin composition of this embodiment can be suitably used in a halftone exposure process.

[0115] In this embodiment, the number average molecular weight (Mn) of the second resin (B) having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and further preferably 1000 to 5000. If the number average molecular weight is 500 or more, the resin is favorable as a resin for photosensitive materials because of appropriate alkali solubility, and if it is 8000 or less, the coating property and developability are favorable.

[0116] In this embodiment, the photoacid generator (D) is preferably PAG-169 (BASF).

[0117] In this embodiment, the first resin (A) is preferably a copolymer containing a structural unit represented by formula (3) and a structural unit represented by formula (2). The structural unit represented by formula (3) and the structural unit represented by formula (2) are as described above.

[0118] In this embodiment, the acid-decomposable group of the first resin (A) is preferably a group represented by formula (7), and R 6 or R 7 One of the two and R 8 and R are more preferably bonded to form a ring structure, and even more preferably R is a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 2-tetrahydrofuranyl group, or a 2-tetrahydropyranyl group. 6 , R 7 and R 8 As mentioned above.

[0119] In the positive photosensitive resin composition of this embodiment, the content of the colorant (C) is preferably 10 parts by mass to 150 parts by mass, more preferably 30 parts by mass to 100 parts by mass, and even more preferably 40 parts by mass to 90 parts by mass, based on 100 parts by mass of the total of the first resin (A) and the second resin (B). If the content of the colorant (C) is 40 parts by mass or more, based on 100 parts by mass of the total of the first resin (A) and the second resin (B), the light-shielding properties in a thick film and the pattern formability of the coating are good, and if it is 150 parts by mass or less, the coating can be colored without impairing the alkali developability.

[0120] One embodiment is a partition wall for an organic electroluminescence device, which comprises a cured product of the positive-type photosensitive resin composition.

[0121] One embodiment is an insulating film for an organic electroluminescence device, which comprises a cured product of the positive-type photosensitive resin composition.

[0122] One embodiment is an organic electroluminescence device comprising a cured product of the positive-type photosensitive resin composition. EXAMPLES

[0123] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

[0124] (1) Raw materials The raw materials used in the examples and comparative examples were produced or obtained as follows.

[0125] The weight average molecular weight and number average molecular weight of the first resin (A), the second resin (B) and other resins 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℃

[0126] [Reference Production Example 1] Production of an alkaline aqueous solution soluble copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer 25.5 g of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko K.K.) and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) as a solvent, and 3.66 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) in a 300 mL three-neck flask. The two obtained solutions were simultaneously dropped into 61.2 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) heated to 85 ° C. under a nitrogen gas atmosphere in a 300 mL three-neck flask over a period of 2 hours, and then reacted at 85 ° C. for 3 hours. The reaction solution cooled to room temperature was dropped into 815 g of toluene to precipitate a copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 90°C for 4 hours to collect 32.4g of white powder. The number average molecular weight of the obtained PCX-02e was 3100 and the weight average molecular weight was 6600.

[0127] [Reference Production Example 2] Production of glycidyl methacrylate and methacrylic acid copolymer (GMA-MAA) 99.5g (0.7 mol) of glycidyl methacrylate (GMA) and 8.6g (0.1 mol) of methacrylic acid (MAA) were completely dissolved in 72.1g of propylene glycol monomethyl ether (PGME), and 7.6g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 7.6g of PGME. The two obtained solutions were simultaneously dropped over 2 hours into 172.6g of PGME heated to 80°C under a nitrogen gas atmosphere in a 500mL three-neck flask, and then reacted by stirring for 2 hours. In this way, a copolymer of glycidyl methacrylate and methacrylic acid (GMA-MAA) with a molar ratio of glycidyl methacrylate to methacrylic acid of 7:1 was obtained in the form of a PGMEA solution with a solid content of 30% by mass. The obtained GMA-MAA has a carboxyl group and an epoxy group in the molecule, and therefore has high self-reactivity, i.e., the ring-opening polymerization of the epoxy group is likely to proceed, so that when reprecipitation and vacuum drying were performed, the molecular weight increased and it was not possible to isolate it. The GMA-MAA solution in PGMEA had low stability, and the molecular weight increased over time, increasing the viscosity of the solution.

[0128] First resin (A) [Production Example 1] Production of the first resin (A) (PCX-02e-EOE) in which the phenolic hydroxyl group is protected with a 1-ethoxyethyl group In a 100 mL three-neck flask, 10.0 g of an aqueous alkali-soluble copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, and 0.60 g of a pyridinium salt of p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid catalyst were dissolved in 50.0 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.). Then, the mixture was ice-cooled under a nitrogen gas atmosphere, and 6.88 g of ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. Then, the mixture was stirred at room temperature for 16 hours. After neutralizing the acid catalyst with a saturated aqueous sodium bicarbonate solution, the water layer was removed. The organic layer was further washed twice with water. Then, tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of toluene to precipitate the product. The precipitate was collected by filtration and vacuum-dried at 80°C for 4 hours to collect 11.0 g of white powder. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20% solids solution of the first resin (A) (PCX-02e-EOE) in which the phenolic hydroxyl groups were protected with 1-ethoxyethyl groups. The number average molecular weight of the obtained PCX-02e-EOE was 4300, the weight average molecular weight was 7900, the proportion of the phenolic hydroxyl groups protected with acid-decomposable groups was 65 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 was 55% 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 heating rate of 10°C / min in a nitrogen gas flow, held for 10 minutes, and then further increased to 400°C at a heating rate of 10°C / min.

[0129] [Production Example 2] Production of the first resin (A) (PCX-02e-Boc) in which the phenolic hydroxyl group is protected with a tert-butoxycarbonyl group In a 100 mL three-neck flask, 10.0 g of an aqueous alkali-soluble copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, and 1.74 g of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a base were dissolved in 50.0 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Then, the mixture was cooled with ice under a nitrogen gas atmosphere, and 3.47 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. Then, the mixture was stirred at room temperature for 16 hours. Then, tetrahydrofuran was distilled off, and the obtained 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 vacuum dried at 80°C for 4 hours to collect 10.3 g of white powder. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20% by mass solids solution of the first resin (A) (PCX-02e-Boc) in which the phenolic hydroxyl groups were protected with tert-butoxycarbonyl groups. The number average molecular weight of the obtained PCX-02e-Boc was 4400, the weight average molecular weight was 7800, the ratio of the phenolic hydroxyl groups protected with acid decomposable groups was 30 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 was 26% of the total number of structural units of the first resin (A). The ratio of the phenolic hydroxyl groups protected with acid decomposable groups was calculated from the weight loss rate (%) of the first resin (A) at 220°C when the temperature was raised from room temperature to 400°C under conditions of a heating rate of 10°C / min in a nitrogen gas flow using a thermogravimetric differential thermal analyzer (TG / DTA6200, Hitachi High-Tech Science Corporation).

[0130] [Production Example 3] Production of the first resin (A) (PCX-02e-THF) in which the phenolic hydroxyl group is protected with a 2-tetrahydrofuranyl group In a 100 mL three-neck flask, 10.0 g of an aqueous alkali-soluble copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, and 0.60 g of a pyridinium salt of p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid catalyst were dissolved in 50.0 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.). Then, the mixture was ice-cooled under a nitrogen gas atmosphere, and 6.69 g of 2,3-dihydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. Then, the mixture was stirred at room temperature for 16 hours. After neutralizing the acid catalyst with a saturated aqueous sodium bicarbonate solution, the water layer was removed. The organic layer was further washed twice with water. Then, the tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of toluene to precipitate the product. The precipitate was collected by filtration and vacuum dried at 80°C for 4 hours to collect 11.0 g of white powder. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20 mass% solids solution of the first resin (A) (PCX-02e-THF) in which the phenolic hydroxyl groups were protected with 2-tetrahydrofuranyl groups. The number average molecular weight of the obtained PCX-02e-THF was 3716, the weight average molecular weight was 6806, the proportion of the phenolic hydroxyl groups protected with acid-decomposable groups was 65 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 was 55% 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 heating rate of 10°C / min in a nitrogen gas flow, held for 10 minutes, and then further increased to 400°C at a heating rate of 10°C / min.

[0131] [Production Example 4] Production of First Resin (A) (PCX-02e-POE) in Which Phenolic Hydroxyl Groups Are Protected with 1-n-Propoxyethyl Groups In a 100 mL three-neck flask, 10.0 g of an aqueous alkali-soluble copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, and 0.60 g of a pyridinium salt of p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid catalyst were dissolved in 50.0 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.). Then, the mixture was cooled on ice under a nitrogen gas atmosphere, and 8.23 ​​g of n-propyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. Then, the mixture was stirred at room temperature for 16 hours. After neutralizing the acid catalyst with a saturated aqueous sodium bicarbonate solution, the water layer was removed. The organic layer was further washed twice with water. Then, tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of toluene to precipitate the product. The precipitate was collected by filtration and vacuum-dried at 80°C for 4 hours to collect 11.0 g of white powder. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20% solids solution of the first resin (A) (PCX-02e-POE) in which the phenolic hydroxyl groups were protected with 1-n-propoxyethyl groups. The number average molecular weight of the obtained PCX-02e-POE was 4550, the weight average molecular weight was 8054, the proportion of the phenolic hydroxyl groups protected with acid-decomposable groups was 65 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 was 55% 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 heating rate of 10°C / min in a nitrogen gas flow, held for 10 minutes, and then further increased to 400°C at a heating rate of 10°C / min.

[0132] Second resin (B) [Production Example 5] Production of second resin (N770OH70) having epoxy groups and phenolic hydroxyl groups In a 300 mL three-neck flask, 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was charged as a solvent, and 37.6 g of EPICLON (registered trademark) N-770 (phenol novolac type epoxy resin manufactured by DIC Corporation, epoxy equivalent 188) was charged as a compound having at least two epoxy groups in one molecule, and dissolved at 60° C. under a nitrogen gas atmosphere. 20.1 g (0.65 equivalents per epoxy equivalent) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added as a hydroxybenzoic acid compound, and 0.173 g (0.660 mmol) of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a reaction catalyst, and the mixture was reacted at 110° C. for 24 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and filtered to obtain 286.5 g of a solution of a second resin (N770OH70) having epoxy groups and phenolic hydroxyl groups. The number average molecular weight of the resulting reaction product was 2400, the weight average molecular weight was 8300, and the epoxy equivalent was 2000.

[0133] [Production Example 6] Production of second resin (N695OH70) having epoxy groups and phenolic hydroxyl groups In a 300 mL three-neck flask, 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was charged as a solvent, and 37.8 g of EPICLON (registered trademark) N-695 (a cresol novolac type epoxy resin manufactured by DIC Corporation, epoxy equivalent 214) was charged as a compound having at least two epoxy groups in one molecule, and dissolved at 60° C. under a nitrogen gas atmosphere. 20.1 g (0.65 equivalents per epoxy equivalent) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added as a hydroxybenzoic acid compound, and 0.166 g (0.660 mmol) of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a reaction catalyst, and the mixture was reacted at 110° C. for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and filtered to obtain 274.2 g of a solution of a second resin (N695OH70) having epoxy groups and phenolic hydroxyl groups. The number average molecular weight of the resulting reaction product was 3000, the weight average molecular weight was 7500, and the epoxy equivalent was 2200.

[0134] [Production Example 7] Production of second resin (N770OH50) having epoxy groups and phenolic hydroxyl groups Except for using 15.4 g of 3,5-dihydroxybenzoic acid, 259.9 g of a solution of a second resin (N770OH50) having an epoxy group and a phenolic hydroxyl group was obtained in the same manner as in Production Example 5. The number average molecular weight of the resulting reaction product was 2000, the weight average molecular weight was 6900, and the epoxy equivalent was 670.

[0135] [Production Example 8] Production of second resin (N695OH50) having epoxy groups and phenolic hydroxyl groups A solution of 256.2 g of a second resin (N695OH50) having epoxy groups and phenolic hydroxyl groups was obtained in the same manner as in Production Example 6, except that 13.9 g of 3,5-dihydroxybenzoic acid was used. The number average molecular weight of the resulting reaction product was 2900, the weight average molecular weight was 6400, and the epoxy equivalent was 820.

[0136] Colorant (C) As the colorant (C), a black dye, VALIFAST (registered trademark) BLACK 3804 (a black dye defined by the CI of Solvent Black 34, manufactured by Orient Chemical Industry Co., Ltd.), NUBIAN (registered trademark) BLACK PA-2802 (a mixture of a black dye and an oil-soluble dye defined by the CI of Solvent Black 27, manufactured by Orient Chemical Industry Co., Ltd.), or VALIFAST (registered trademark) BLACK 3820 (a black dye defined by the CI of Solvent Black 27, manufactured by Orient Chemical Industry Co., Ltd.) was used.

[0137] Photoacid generator (D) The photoacid generator (D) used was PAI-101 (manufactured by Midori Chemical Co., Ltd., CAS No. 82424-53-1), an oxime-based photoacid generator. PAI-101 generates p-toluenesulfonic acid (pKa = -2.8) when irradiated with light. The structure of PAI-101 is shown below.

[0138] [ka]

[0139] The photoacid generator (D) used was an oxime-based photoacid generator, PAG-103 (2-[2-(propylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, manufactured by BASF, CAS No. 852246-55-0). PAG-103 generates 1-propanesulfonic acid (pKa=-2.8) upon irradiation with light. The structure of PAG-103 is shown below.

[0140] [ka]

[0141] The photoacid generator (D) used was PAG-169 (BASF), an oxime-based photoacid generator. PAG-169 generates trifluoromethanesulfonic acid (pKa = -13) when irradiated with light.

[0142] The quinone diazide compound used was 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.

[0143] [ka]

[0144] Phloroglucinol or 2,4-dihydroxybenzoic acid was used as the solubility enhancer (E).

[0145] Megafac (registered trademark) F-559 (fluorine-based surfactant, manufactured by DIC Corporation) was used as the surfactant (leveling agent).

[0146] As the solvent (G), a mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA=40:60 (mass ratio), or GBL:PGMEA=70:30 (mass ratio)) was used.

[0147] Other resins used were PCX-02e of Reference Production Example 1, GMA-MAA of Reference Production Example 2, EPICLON (registered trademark) N-770 (phenol novolac type epoxy resin manufactured by DIC Corporation, epoxy equivalent 188), and SHONOL (registered trademark) BRG-556 (phenol novolac resin manufactured by Aica Kogyo Co., Ltd.).

[0148] (2) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[0149] [OD value after heating] A glass substrate (size 100 mm x 100 mm x 1 mm) was spin-coated with a positive photosensitive resin composition so that the dry film thickness was about 1.5 μm (Examples 1 to 13, Comparative Examples 1 to 4) or about 3.8 μm (Examples 14 to 19), and the solvent was dried by heating on a hot plate at 120° C. for 80 seconds. Then, the coating was obtained by curing at 250° C. for 60 minutes in a nitrogen gas atmosphere. The OD value of the cured coating was measured with a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.), and was converted to an OD value per 1 μm of coating thickness by correcting with the OD value of the glass alone. The thickness of the coating was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Inc.).

[0150] [Solubility of unexposed areas] A glass substrate (size 100 mm x 100 mm x 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 2.0 μm, and the solvent was dried by heating on a hot plate at 120 ° C. for 80 seconds. The dry film thickness was measured using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.), and then alkali development was performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device (AD-1200, Takizawa Sangyo Co., Ltd.). The film thickness after alkali development was measured again using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.), and the film thickness (μm) dissolved before and after development was calculated as the solubility of the unexposed area.

[0151] [Solubility of exposed area] A positive photosensitive resin composition was bar-coated onto a glass substrate (size 100 mm x 100 mm x 1 mm) so that the dry film thickness was 2.0 μm, and pre-baked by heating on a hot plate at 100° C. for 1 minute. The dry film thickness was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Inc.), and then the dry film thickness was measured using an exposure device (product name Multilight ML-251A / B, manufactured by Ushio Inc.) incorporating an ultra-high pressure mercury lamp, and the film was exposed to 100 mJ / cm 2 through a mercury exposure bandpass filter (product name HB0365, manufactured by Asahi Spectroscopic Co., Ltd.) and a quartz photomask (having line and space (L / S) patterns of 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, and 500 μm). 2 The exposure was measured using an ultraviolet integrating light meter (product name UIT-150 light receiving part UVD-S365, manufactured by Ushio Inc.). After exposure, the film was heated on a hot plate at 100°C or 120°C for 3 or 5 minutes to perform PEB. Then, using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkaline development was performed for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. The film thickness after alkaline development was measured again using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Inc.), and the film thickness (μm) dissolved before and after development was calculated as the solubility of the exposed area.

[0152] [Solubility difference] The solubility difference (μm) was calculated by subtracting the solubility (μm) of the unexposed area from the solubility (μm) of the exposed area. A larger solubility difference means higher sensitivity and superior pattern formability.

[0153] [10μm hole pattern formation] A positive photosensitive resin composition was bar-coated onto a glass substrate (size 100 mm × 100 mm × 1 mm) to a dry film thickness of 3.8 μm, and after vacuum drying for 90 seconds, the composition was pre-baked by heating on a hot plate with a lid at 110°C for 2 minutes. The composition was exposed to 100 mJ / cm2 through a bandpass filter for mercury exposure (product name HB0365, manufactured by Asahi Spectroscopic Co., Ltd.) and a quartz photomask (having a φ10 μm pattern) using an exposure device (product name Multilight ML-251A / B, manufactured by Ushio Inc.) equipped with an ultra-high pressure mercury lamp. 2 The exposure was performed under the following conditions. The exposure dose was measured using an ultraviolet integrating light meter (product name UIT-150 light receiving part UVD-S365, manufactured by Ushio Electric Co., Ltd.). After the exposure, the film was heated on a hot plate with a lid at 115 to 130°C for 3 or 4 minutes to perform PEB. Then, using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkaline development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Furthermore, the coating film was heated at 250°C for 60 minutes in an inert oven (DN411I, manufactured by Yamato Scientific Co., Ltd.) to cure. The film thickness of the cured coating film was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.), and the formed holes were observed with a microscope (VHX-6000, manufactured by Keyence Corporation). A film thickness of 3.0 μm or more and a hole diameter of 10 μm or more was judged as good, and a film thickness of 2.9 μm or less or a hole diameter of 9 μm or less was judged as poor.

[0154] [Step pattern formation] A positive photosensitive resin composition was bar-coated onto a glass substrate (size 100 mm × 100 mm × 1 mm) to a dry film thickness of 3.8 μm, vacuum dried for 90 seconds, and then pre-baked by heating on a hot plate with a lid at 110°C for 2 minutes. The composition was exposed to 100 mJ / cm2 through a mercury exposure bandpass filter (product name HB0365, manufactured by Asahi Spectroscopic Co., Ltd.) and a quartz halftone photomask (having a hole with a diameter of 10.5 μm and a transmittance of 100% in the center, and a ring pattern with an outer diameter of 30.5 μm and a width of 10 μm and a transmittance of 25% on the outside of the hole) using an exposure device (product name Multilight ML-251A / B, manufactured by Ushio Inc.) incorporating an ultra-high pressure mercury lamp. 2 The exposure was performed at the following temperature. The exposure dose was measured using an ultraviolet integrating light meter (product name UIT-150 light receiving part UVD-S365, manufactured by Ushio Electric Co., Ltd.). After the exposure, the film was heated on a hot plate with a lid at 110 to 130°C for 3 or 4 minutes to perform PEB. Then, using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkaline development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Furthermore, the film was heated at 250°C for 60 minutes in an inert oven (DN411I, manufactured by Yamato Scientific Co., Ltd.) to cure. The step pattern formed on the cured coating film was observed with a shape analysis laser microscope (product name VK-X200, manufactured by Keyence Co., Ltd.), and a step width of 20 μm or more was judged to be good, and one less than 20 μm was judged to be bad.

[0155] (3) Preparation and evaluation of positive-type photosensitive resin composition [Examples 1 to 13, Comparative Examples 1 to 4] The first resin (A), the second resin (B) and optionally other resins (optional component (F)) were mixed and dissolved in the composition shown in Table 1 or Table 2, and the colorant (C), photoacid generator (D) and quinone diazide compound (optional component (F)), dissolution promoter (E), surfactant (optional component (F)) and GBL / PGMEA mixed solvent (G) shown in Table 1 or Table 2 were added to the obtained solution and further mixed. After visually confirming that the components were 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 solid content concentration of about 12 mass %. The parts by mass of the composition in Tables 1 and 2 are solid content equivalent values. Tables 1 and 2 also show the protection rate of the phenolic hydroxyl group of the first resin (A) based on the total of the alkali-soluble functional groups of the first resin (A) and the second resin (B). The evaluation results of the positive photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2 are shown in Table 1. The evaluation results of the positive photosensitive resin compositions of Examples 10 to 13 and Comparative Examples 3 and 4 are shown in Table 2.

[0156] [Table 1-1]

[0157] [Table 1-2]

[0158] [Table 2]

[0159] [Examples 14 to 19] The first resin (A) and the second resin (B) were mixed and dissolved in the composition shown in Table 3, and the colorant (C), photoacid generator (D), dissolution promoter (E), and GBL / PGMEA mixed solvent (G) shown in Table 3 were added to the obtained solution and further mixed. After visually confirming that the components were 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 solid content concentration of about 12 mass %. The parts by mass of the composition in Table 3 are solid content equivalent values. Table 3 also shows the protection rate of the phenolic hydroxyl group of the first resin (A) based on the total of the alkali-soluble functional groups of the first resin (A) and the second resin (B), and the epoxy equivalent of the second resin (B). The evaluation results of the positive photosensitive resin compositions of Examples 14 to 19 are shown in Table 3.

[0160] [Table 3] [Industrial Applicability]

[0161] The positive-type photosensitive resin composition according to the present disclosure can be suitably used in radiation lithography for forming a partition wall or an insulating film of an organic EL element. An organic EL element having a partition wall or an insulating film formed from the positive-type photosensitive resin composition according to the present disclosure is suitably used as an electronic component of a display device exhibiting good contrast.

Claims

1. a first resin (A) having a plurality of phenolic hydroxyl groups, at least a portion of which is protected by an acid-decomposable group; a second resin (B) having an epoxy group and a phenolic hydroxyl group; At least one colorant (C) selected from the group consisting of black dyes and black pigments; A photoacid generator (D); Including, 10 mol % to 95 mol % of the phenolic hydroxyl groups of the first resin (A) are protected with the acid-decomposable group, The second resin (B) is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and is represented by the formula (5): 【Chemistry 1】 (In formula (5), 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.) is a compound having the structure The compound having at least two epoxy groups in one molecule is a novolac type epoxy resin.

2. 2. The positive photosensitive resin composition according to claim 1, wherein the first resin (A) is an alkaline aqueous solution-soluble copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, the copolymer having a plurality of phenolic hydroxyl groups, at least a portion of the plurality of phenolic hydroxyl groups being protected by the acid-decomposable group.

3. 3. The positive photosensitive resin composition according to claim 1, wherein the acid-decomposable group of the first resin (A) is a 1-alkoxyalkyl group.

4. The first resin (A) is represented by the formula (3): 【Chemistry 2】 (In formula (3), R １ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 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 the first resin (A) has at least one structural unit represented by the following formula: wherein s is an integer of 1 or more.

5. The first resin (A) is represented by the formula (2): 【Chemistry 3】 (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 alkyl 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 or a cyclic alkyl group having 4 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The positive photosensitive resin composition according to any one of claims 2 to 4, having a structural unit represented by the following formula:

6. 6. The positive photosensitive resin composition according to claim 1, wherein 5 mol % to 65 mol % of the phenolic hydroxyl groups of the first resin (A) are protected with the acid-decomposable group, based on the total amount of alkali-soluble functional groups of the first resin (A) and the second resin (B).

7. 7. The positive photosensitive resin composition according to claim 1, comprising 20% ​​by mass to 90% by mass of the first resin (A) based on the total mass of the first resin (A) and the second resin (B).

8. 8. The positive photosensitive resin composition according to claim 1, comprising 10 parts by mass to 150 parts by mass of the colorant (C) based on a total of 100 parts by mass of the first resin (A) and the second resin (B).

9. The positive photosensitive resin composition according to any one of claims 1 to 8, wherein the photoacid generator (D) is contained in an amount of 0.1 parts by mass to 85 parts by mass based on a total of 100 parts by mass of the first resin (A) and the second resin (B).

10. 10. The positive photosensitive resin composition according to claim 1, 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.

11. The positive photosensitive resin composition according to any one of claims 1 to 10, wherein the hydroxybenzoic acid compound is a dihydroxybenzoic acid compound.

12. The positive photosensitive resin composition according to any one of claims 1 to 11, wherein the second resin (B) has an epoxy equivalent of 300 to 1800, and the photoacid generator (D) generates trifluoromethanesulfonic acid upon irradiation with light.

13. A partition wall for an organic electroluminescence device, comprising a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 12.

14. An insulating film for an organic electroluminescence device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 12.

15. An organic EL device comprising a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 12.

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