Positive photosensitive resin composition and organic EL element partition wall

Abstract

To provide a photosensitive resin composition that has high sensitivity and suppresses pin-mura (uneven thickness) of a coating film obtained therefrom.SOLUTION: A positive photosensitive resin composition contains a binder resin (A), a photoacid generator (B), and a solvent (C), with the solvent (C) containing (c1) γ-butyrolactone, (c2) 1-methoxy-2-propyl acetate, and (c3) acetate ester represented by formula (7). (In the formula (7), R5 is a C1 to 12 hydrocarbon group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a positive photosensitive resin composition, and to an organic EL device partition wall, an organic EL device insulating film, and an organic EL device each using the same. [Background technology]

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

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

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

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

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

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

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

[0009] The solvent used in a photosensitive resin composition affects its performance. Patent Document 5 describes that the use of a solvent containing diacetone alcohol and an acetic acid ester improves sensitivity and wettability onto a substrate. Patent Document 6 shows that the use of multiple solvents with different boiling points and resin solubilities improves sensitivity by making the coating film non-uniform. Patent Document 7 shows that high sensitivity is achieved by using multiple specific solvents in combination. However, these examples have low colorability and do not provide sufficient light-blocking properties.

[0010] Patent Document 8 describes a photosensitive resin composition with high light-blocking properties that is colored with an azo black dye or a carbon black pigment. However, the photosensitivity relative to the light-blocking properties is only shown in an example in which a single solvent is used, and no detailed investigation into the use of multiple solvents is given. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-281440 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-116536 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-237310 [Patent Document 4] International Publication No. 2017 / 069172 [Patent Document 5] Japanese Patent Application Publication No. 8-76372 [Patent Document 6] Japanese Patent Application Laid-Open No. 2009-139537 [Patent Document 7] Japanese Patent Application Publication No. 8-320557 [Patent Document 8] Special Publication No. 2013-533508 Summary of the Invention [Problem to be solved by the invention]

[0012] In the photosensitive resin composition used to form a colored partition wall material, a considerable amount of colorant must be used to sufficiently enhance the light-shielding properties of the cured film. When such a large amount of colorant is used, the radiation irradiated onto the coating of the photosensitive resin composition is absorbed by the colorant, reducing the effective intensity of the radiation in the coating and resulting in insufficient exposure of the photosensitive resin composition, resulting in poor pattern formability.

[0013] In particular, when attempting to form a thick coating, e.g., a coating having a thickness of 2 to 3 μm, using a photosensitive resin composition containing a black agent, the amount of radiation reaching the bottom of the coating in the exposed area is significantly reduced due to the absorption of radiation by the radiation-sensitive compound in addition to the black agent. Therefore, in a positive-tone film, the bottom of the coating in the exposed area may not be sufficiently alkaline-soluble, resulting in the generation of resin residue during development, or a large amount of photosensitive resin composition may be consumed to obtain a coating of the desired thickness, i.e., the film retention rate may be reduced. On the other hand, in a negative-tone film, the bottom of the coating in the exposed area may not be sufficiently insolubilized, resulting in film peeling during development. Therefore, there is a strong demand for a photosensitive resin composition containing a black agent that can impart a high optical density (OD value) to the cured coating while increasing the thickness of the cured coating.

[0014] Furthermore, when a coating is formed using a photosensitive resin composition containing a black agent, a considerable amount of colorant is used, which can cause unevenness such as pin marks in the coating.

[0015] An object of the present invention is to provide a photosensitive resin composition that has high sensitivity and suppresses pin unevenness in the resulting coating. [Means for solving the problem]

[0016] The present inventors have found that, in a positive photosensitive resin composition, by using a specific mixed solvent as the solvent contained in the composition, it is possible to increase the sensitivity of the positive photosensitive resin composition while suppressing pin unevenness on the surface of the resulting coating film.

[0017] That is, the present invention includes the following aspects. [1] a binder resin (A); a photoacid generator (B); a solvent (C); A positive photosensitive resin composition comprising the solvent (C): (c1) γ-butyrolactone, (c2) 1-methoxy-2-propyl acetate, and (c3) Acetate ester represented by the following formula (7): [ka] (In equation (7), R 5 represents a hydrocarbon group having 1 to 12 carbon atoms. A positive photosensitive resin composition comprising: [2] The positive photosensitive resin composition according to [1], wherein the (c3) acetate ester is at least one selected from the group consisting of n-butyl acetate and i-butyl acetate. [3] The positive photosensitive resin composition according to [1] or [2], wherein the content of (c1) γ-butyrolactone is 10% by mass to 60% by mass, the content of (c2) 1-methoxy-2-propyl acetate is 20% by mass to 80% by mass, and the content of (c3) acetic acid ester is 5% by mass to 40% by mass, relative to 100% by mass of the solvent (C). [4] The positive photosensitive resin composition according to any one of [1] to [3], wherein the solvent (C) further contains at least one amide compound (c4) selected from the group consisting of formula (8), formula (9), and formula (10). [ka] (In equation (8), R a is a hydrocarbon group having 1 to 8 carbon atoms, which may have an alkoxy group having 1 to 6 carbon atoms as a substituent, and R b and R c are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R a , R b , and R c may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent.) [ka] (In equation (9), R d is a hydrocarbon group having 1 to 6 carbon atoms, and R e and R fare each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R d , R e , and R f may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent.) [ka] (In Equation (10), R g , R h , R i , and R j are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R g , R h , R i , and R j may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent.) [5] The positive photosensitive resin composition according to [4], wherein the content of the amide compound (c4) is 0.01% by mass to 10% by mass relative to 100% by mass of the solvent (C). [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the binder resin (A) contains a first resin (D) having a plurality of phenolic hydroxyl groups. [7] The first resin (D) is a compound 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. The positive photosensitive resin composition according to [6], having a structural unit represented by the following formula: [8] The first resin (D) is a compound represented by the formula (2): [ka] (In formula (2), R 2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The positive photosensitive resin composition according to [7], having a structural unit represented by the following formula: [9] The positive photosensitive resin composition according to any one of [6] to [8], wherein the binder resin (A) further contains a second resin (E) having an epoxy group and a phenolic hydroxyl group.

[10] The second resin (E) is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid compound, and is represented by the formula (3): [ka] (In formula (3), 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 [9], wherein the compound has the structure:

[11] The positive photosensitive resin composition according to

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

[12] The positive photosensitive resin composition according to

[10] or

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

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

[12] , wherein the photoacid generator (B) contains a quinone diazide compound.

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

[13] , which contains at least one colorant (F) selected from the group consisting of black dyes and black pigments.

[15] The positive photosensitive resin composition according to

[14] , 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.

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

[15] .

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

[15] . [Effects of the Invention]

[0018] In the present invention, by using a solvent containing (c1) γ-butyrolactone, (c2) 1-methoxy-2-propyl acetate, and (c3) an acetic acid ester, it is possible to obtain a positive photosensitive resin composition that has high sensitivity and suppresses pin unevenness in the resulting coating film. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below.

[0020] In this 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 a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. The term "alkali-soluble functional group" refers to a group that imparts such alkali-solubility to the positive photosensitive resin composition or a component thereof, or a coating or cured coating of the positive photosensitive resin composition. Examples of alkali-soluble functional groups include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group.

[0021] In the present disclosure, the term "radically polymerizable functional group" refers to an ethylenically unsaturated group.

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

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

[0024] In the present disclosure, the term "resin component" refers to a binder resin (A). The binder resin (A) may contain a first resin (D) described below, and may further contain a second resin (E) and / or other resins.

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

[0026] <Positive-type photosensitive resin composition> A positive photosensitive resin composition according to one embodiment contains a binder resin (A), a photoacid generator (B), and a solvent (C) containing specific components.

[0027] <Solvent (C)> In one embodiment, the positive photosensitive resin composition uses a mixed solvent consisting of three or more organic solvents including (c1) γ-butyrolactone, (c2) 1-methoxy-2-propyl acetate, and (c3) an acetic acid ester.

[0028] [(c1) γ-butyrolactone] In one embodiment, the solvent component contained in the positive photosensitive resin composition is (c1) γ-butyrolactone. By using (c1) γ-butyrolactone as the solvent, the solid content in the resin composition can be well dissolved, and the uniformity of the coating film can be improved.

[0029] [(c2) 1-Methoxy-2-propyl acetate] In one embodiment, the solvent component contained in the positive photosensitive resin composition is (c2) 1-methoxy-2-propyl acetate. By using (c2) 1-methoxy-2-propyl acetate as a solvent, (c2) 1-methoxy-2-propyl acetate evaporates appropriately during the coating process, preventing excessive dissolution of unexposed areas due to excess solvent remaining in the coating film.

[0030] [(c3) Acetate ester] The solvent component contained in the positive photosensitive resin composition of one embodiment is an acetic acid ester (c3) represented by the following formula (7). [ka] (In equation (7), R 5 represents a hydrocarbon group having 1 to 12 carbon atoms.

[0031] R in Equation (7) 5 is a hydrocarbon group having 1 to 12 carbon atoms. 5 When the number of carbon atoms in R is 1 or more, it is located in the vicinity of the hydrophobic component, and thus has sufficient hydrophobicity, resulting in high photosensitivity. 5 When the number of carbon atoms in R is 12 or less, the effect of the acetoxy group as a hydrogen acceptor is not impaired, and the effect of improving the photosensitivity can be obtained. 5 The number of carbon atoms is more preferably 1 to 10, and even more preferably 2 to 8.

[0032] R 5does not contain a heteroatom, and the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group may be saturated or unsaturated, but a saturated hydrocarbon group is preferred in terms of interaction with the resin. 5 is more preferably an alkyl group having 1 to 12 carbon atoms.

[0033] When a positive-tone photosensitive resin composition is applied, most of the (c3) acetate ester evaporates during the drying process, but trace amounts are thought to remain in the coating film. The (c3) acetate ester remaining in the coating film is thought to be located between the alkali-soluble functional group and the hydrophobic component, with the acetoxy group acting as a hydrogen bond acceptor to form hydrogen bonds with the alkali-soluble functional group, and the hydrocarbon functional group locating near the hydrophobic component with low alkali solubility due to hydrophobic interactions. This is expected to suppress alkali solubility through hydrogen bonding in unexposed areas. In exposed areas, the (c3) acetate ester dissolves from the coating film as the alkali-soluble group-containing component dissolves, amplifying the so-called stone wall effect and promoting the dissolution of adjacent hydrophobic components with low alkali solubility. The stone wall effect is the effect of dissolving highly soluble components into the developer, increasing the contact area of ​​the less soluble components with the developer, thereby accelerating their dissolution. Since (c3) acetate ester increases the difference in alkali solubility between the unexposed and exposed areas, a highly sensitive positive photosensitive resin composition can be obtained by using (c3) acetate ester as a solvent.

[0034] Specific examples of (c3) acetate esters include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, sec-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, 2-ethylhexyl acetate, cyclopentyl acetate, cyclohexyl acetate, vinyl acetate, allyl acetate, and phenyl acetate. Among these, any one selected from the group consisting of ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, sec-pentyl acetate, allyl acetate, and phenyl acetate is more preferred. These (c3) acetate esters can be used alone or in combination of two or more.

[0035] Among these, (c3) acetate ester is particularly preferably at least one selected from the group consisting of n-butyl acetate and i-butyl acetate.

[0036] In one embodiment, the solvent for the positive photosensitive resin composition contains (c1) γ-butyrolactone in an amount of 10% by mass to 60% by mass, preferably 15% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass, based on 100% by mass of the entire solvent. When the (c1) γ-butyrolactone content is 10% by mass or more, precipitation of solutes during the drying process can be suppressed, resulting in a coating film with a good surface. When the (c1) γ-butyrolactone content is 60% by mass or less, the solubility of unexposed areas can be kept low, thereby maintaining a high residual film rate.

[0037] In one embodiment, the solvent for the positive photosensitive resin composition contains (c2) 1-methoxy-2-propyl acetate in an amount of 20% by mass to 80% by mass, preferably 30% by mass to 70% by mass, and more preferably 40% by mass to 60% by mass, based on 100% by mass of the entire solvent. When the content of (c2) 1-methoxy-2-propyl acetate is 20% by mass or more, a good pattern can be formed. When the content of (c2) 1-methoxy-2-propyl acetate is 80% by mass or less, precipitation of the solute during coating can be suppressed, resulting in a coating film with a good surface.

[0038] In one embodiment, the solvent for the positive photosensitive resin composition contains (c3) acetic acid ester in an amount of 5% by mass to 40% by mass, preferably 7% by mass to 35% by mass, and more preferably 10% by mass to 30% by mass, based on 100% by mass of the entire solvent. When the content of (c3) acetic acid ester is 5% by mass or more, the positive photosensitive resin composition exhibits high sensitivity and good coatability. When the content of (c3) acetic acid ester is 40% by mass or less, precipitation of solutes during coating can be suppressed, and a coating film with a good surface can be obtained.

[0039] [(c4) Amide compounds] In one embodiment, the positive photosensitive resin composition may contain, as the solvent (C), an amide compound (c4) in addition to the above-mentioned compounds (c1) to (c3). In the present disclosure, the "amide compound" includes carbamates and ureas. The amide compound (c4) is preferably at least one compound selected from the group consisting of the following formulas (8), (9), and (10):

[0040] [ka] (In equation (8), R a is a hydrocarbon group having 1 to 8 carbon atoms, which may have an alkoxy group having 1 to 6 carbon atoms as a substituent, and R b and R c are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R a , R b, and R c may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent.)

[0041] In equation (8), R a The hydrocarbon group represented by R may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. a The hydrocarbon group represented by the formula (I) is preferably an aliphatic hydrocarbon group, more preferably an alkyl group.

[0042] In equation (8), R b and R c are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. R b and R c are each independently preferably an aliphatic hydrocarbon group, more preferably an alkyl group.

[0043] In equation (8), R a , R b , and R c However, when they are bonded in any combination to form a ring structure, the ring structure is preferably a 5- to 7-membered ring. a and R b , or R a and R c More preferably, they are cyclic amides bonded to each other.

[0044] [ka] (In equation (9), R d is a hydrocarbon group having 1 to 6 carbon atoms, and R e and R f are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R d , Re , and R f may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent.)

[0045] In equation (9), R d The hydrocarbon group represented by R may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. d The hydrocarbon group represented by the formula (I) is preferably an aliphatic hydrocarbon group, more preferably an alkyl group.

[0046] In equation (9), R e and R f are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. R e and R f are each independently preferably an aliphatic hydrocarbon group, more preferably an alkyl group.

[0047] In equation (9), R d , R e , and R f However, when they are bonded in any combination to form a ring structure, the ring structure is preferably a 5- to 7-membered ring. d and R e , or R d and R f More preferably, they are cyclic carbamates bonded to each other.

[0048] [ka] (In Equation (10), R g , R h , R i , and R j are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R g, R h , R i , and R j may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent.)

[0049] In equation (10), R g , R h , R i , and R j are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. R g , R h , R i , and R j are each independently preferably an aliphatic hydrocarbon group, more preferably an alkyl group.

[0050] In equation (10), R g , R h , R i , and R j However, when they are bonded in any combination to form a ring structure, the ring structure is preferably a 5- to 7-membered ring. g and R i , R g and R j , R h and R i , or R h and R j More preferably, they are cyclic ureas bonded to each other.

[0051] The amide compound (c4) acts as a hydrogen bond acceptor and is positioned to surround the highly alkali-soluble component in the coating film by forming hydrogen bonds without impairing the acidity of the alkali-soluble component, thereby suppressing alkali dissolution in the unexposed areas and strengthening the stonewall effect in the exposed areas, which collapses the surrounding area as the highly alkali-soluble component dissolves, thereby significantly increasing photosensitivity.

[0052] The (c4) amide compound preferably has a boiling point of 170°C or higher and is a liquid at room temperature. When the boiling point is 170°C or higher, the (c4) amide compound remains sufficiently in the coating film, thereby improving the photosensitivity. When the (c4) amide compound is a liquid at room temperature, a uniform coating film can be formed.

[0053] Specific examples of (c4) amide compounds include N,N-diethylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, N,N-dimethylbutanamide, N,N-dimethylisobutyramide, N,N-diethylbutanamide, 3-methoxy-N,N-dimethylbutanamide, 3-ethoxy-N,N-dimethylbutanamide, 4-methoxy-N,N-dimethylbutanamide, and 4-ethoxy-N,N-dimethylbutane. Amides, N,N-dimethylpentanamide, N,N-diethylpentanamide, N,N-dimethylhexanamide, N,N-diethylhexanamide, N,N-dimethylheptanamide, N,N-diethylheptanamide, 1-acetylpyrrolidine, 1-acetylpiperidine, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-pentyl-2-pyrrolidone, 1-hexyl-2-pyrrolidone, 1-cyclopentyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1 -Methyl-2-piperidone, 1-ethyl-2-piperidone, 1-propyl-2-piperidone, 1-butyl-2-piperidone, 1-pentyl-2-piperidone, 1-hexyl-2-piperidone, 1-cyclopentyl-2-piperidone, 1-cyclohexyl-2-piperidone, 1,5-dimethyl-2-piperidone, N-methyl-ε-caprolactam, N-ethyl-ε-caprolactam, N-propyl-ε-caprolactam, 1-methoxycarbonylpiperidine, 1-ethoxycarbonylpiperidine, 1-propyloxycarbonylpiperidine, 3-methyl-2 -oxazolidone, 3-ethyl-2-oxazolidone, 3-propyl-2-oxazolidone, 3-butyl-2-oxazolidone, 3-pentyl-2-oxazolidone, 3-hexyl-2-oxazolidone, 3-cyclopentyl-2-oxazolidone, 3-cyclohexyl-2-oxazolidone, tetramethylurea, 1,1,3,3-tetraethylurea, 1,1,3,3-tetrapropylurea, 1,1,3,3-tetrabutylurea, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and 1,3-diethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone. These amide compounds may be used alone or in combination of two or more.

[0054] Among the above, the (c4) amide compound is preferably at least one selected from the group consisting of 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidone, 3-methoxy-N,N-dimethylpropionamide, and 1-cyclohexyl-2-pyrrolidone.

[0055] The content of the (c4) amide compound is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and even more preferably 0.1% by mass to 5% by mass, based on 100% by mass of the entire solvent. If the content of the (c4) amide compound is 0.01% by mass or more, a sufficient effect of improving photosensitivity can be obtained. If the content of the (c4) amide compound is 10% by mass or less, excessive dissolution of unexposed areas due to excess solvent remaining in the coating film can be prevented.

[0056] In one embodiment, the positive photosensitive resin composition may contain a solvent other than the above (c1) to (c3) and (c4) amide compound. The other solvent may be selected arbitrarily without any particular limitation, but preferably does not contain a hydrocarbon solvent or an alcohol solvent having a boiling point of 160°C or higher. When the positive photosensitive resin composition does not contain a hydrocarbon solvent or an alcohol solvent having a boiling point of 160°C or higher, the interaction of the (c3) acetate ester in the coating film obtained from the positive photosensitive resin composition is less likely to be inhibited, and the photosensitivity improvement effect is more likely to be achieved.

[0057] Other solvents include, for example, carbonate esters such as propylene carbonate, and acetate esters containing an ether bond such as diethylene glycol monoethyl ether acetate and diethylene glycol mono-n-butyl ether acetate.

[0058] The content of other solvents other than the above (c1) to (c3) and (c4) amide compounds is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 0% by mass (no other solvents included), based on 100% by mass of the entire solvent (C).

[0059] In one embodiment, the positive photosensitive resin composition contains, relative to 100% by mass of the solvent (C), the content of (c1) γ-butyrolactone is 10% by mass to 60% by mass, the content of (c2) 1-methoxy-2-propyl acetate is 20% by mass to 80% by mass, and the content of (c3) acetic acid ester is 5% by mass to 40% by mass.

[0060] In another embodiment, the positive photosensitive resin composition has, relative to 100 mass% of the solvent (C), the content of (c1) γ-butyrolactone is 10 mass% to 50 mass%, the content of (c2) 1-methoxy-2-propyl acetate is 20 mass% to 80 mass%, the content of (c3) acetic acid ester is 5 mass% to 40 mass%, and the content of (c4) amide compound is 0.01 mass% to 10 mass%.

[0061] <Binder resin (A)> The binder resin (A) is not particularly limited, and may or may not have an alkali-soluble functional group. Among these, it is preferable that the binder resin (A) has an alkali-soluble functional group, and that the binder resin (A) itself is alkali-soluble. Examples of the alkali-soluble functional group include, but are not limited to, a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group. The binder resin (A) may have two or more types of alkali-soluble functional groups.

[0062] In one embodiment, the positive photosensitive resin composition preferably contains, as the binder resin (A), a first resin (D) having a plurality of phenolic hydroxyl groups, and more preferably a second resin (E) having epoxy groups and phenolic hydroxyl groups. Note that a resin having epoxy groups and phenolic hydroxyl groups may be used as the first resin (D), and in this case, the second resin (E) is a resin different from the first resin (D).

[0063] The binder resin (A) may contain a resin other than the first resin (D) and the second resin (E), such as an acrylic resin, a polystyrene resin, an epoxy resin other than the second resin (E), a polyamide resin, a phenolic resin other than the first resin (D), a polyimide resin, a polyamic acid resin, a polybenzoxazole resin, a polybenzoxazole resin precursor, a silicone resin, a cyclic olefin polymer, a cardo resin, or a derivative of any of these resins. These resins may or may not have an alkali-soluble functional group.

[0064] [First resin (D) having multiple phenolic hydroxyl groups] The first resin (D) is not particularly limited as long as it has a plurality of phenolic hydroxyl groups. The first resin (D) may have an alkali-soluble functional group other than the phenolic hydroxyl group, such as at least one selected from the group consisting of a carboxy group, an alcoholic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group.

[0065] Examples of the first resin (D) include polystyrene resins, epoxy resins, polyamide resins, phenolic resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins, all of which have multiple phenolic hydroxyl groups. Examples of phenolic resin derivatives include polyalkenylphenolic resins in which an alkenyl group is bonded to a benzene ring, and examples of polystyrene resin derivatives include hydroxypolystyrene resin derivatives in which a phenolic hydroxyl group and a hydroxyalkyl group or an alkoxy group are bonded to a benzene ring. The first resin (D) may also be a homopolymer or copolymer of a polymerizable monomer having a phenolic hydroxyl group. These first resins (D) may be used alone or in combination of two or more. The first resin (D) may have a radically polymerizable functional group. In one embodiment, the first resin (D) has a (meth)acryloyloxy group, an allyl group, or a methallyl group as the radically polymerizable functional group.

[0066] In one embodiment, the first resin (D) is an alkali-soluble copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer, and the alkali-soluble copolymer has multiple phenolic hydroxyl groups. The alkali-soluble copolymer may further have an alkali-soluble functional group other than the phenolic hydroxyl group, such as a carboxyl group, an alcoholic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, or a mercapto group. Examples of the polymerizable functional group possessed by the polymerizable monomer include radically polymerizable functional groups, such as CH═CH—, CH═C(CH)—, CH═CHCO—, CH═C(CH)CO—, and —OC—CH═CH—CO—.

[0067] The first resin (D) can be produced, for example, by radical polymerization of a polymerizable monomer having a phenolic hydroxyl group with another polymerizable monomer. After synthesizing a copolymer by radical polymerization, the phenolic hydroxyl group may be added to the copolymer. Examples of polymerizable monomers having a phenolic hydroxyl group include 4-hydroxystyrene, 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, and 4-hydroxyphenyl maleimide. Other polymerizable monomers include, for example, polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, acrylamide, acrylonitrile, vinyl alcohol ether compounds such as vinyl-n-butyl ether, alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, isobutyl acrylate, methyl ... Examples of suitable maleimides include (meth)acrylic acid esters such as runyl(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.

[0068] From the viewpoint of heat resistance, etc., the first resin (D) preferably has one or more types of cyclic structures such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure.

[0069] As a polymerizable monomer having a phenolic hydroxyl group, after polymerization, the following formula (1) [ka] In formula (1), it is preferable to form a structural unit represented by the formula: 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.

[0070] In formula (1), R 1 is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, more preferably 1. As such a polymerizable monomer having a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferred.

[0071] Other polymerizable monomers include those represented by the formula (2) after polymerization. [ka] In formula (2), it is preferable to form a structural unit represented by the formula: 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0072] In equation (2), R 2 and R 3 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. 4is preferably a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group. As such other polymerizable monomers, phenylmaleimide and cyclohexylmaleimide are particularly preferred.

[0073] In one embodiment, the first resin (D) 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. It has a structural unit represented by the following formula:

[0074] In one embodiment, the first resin (D) comprises a structural unit represented by the above formula (1) and a structural unit represented by the formula (2) [ka] (In formula (2), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. It has a structural unit represented by the following formula:

[0075] It is particularly preferred that the first resin (D) uses 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, shape retention and developability can be improved, and outgassing can be reduced.

[0076] The polymerization initiator used when producing the first resin (D) by radical polymerization is not limited to the following, but may be an azo polymerization initiator such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), or 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN); dicumyl peroxide; 2,5-dimethyl-2,5-di(tert-butyl) Examples of peroxide polymerization initiators that can be used include peroxide polymerization initiators having a 10-hour half-life temperature of 100 to 170°C, such as di-tert-butylperoxyhexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide, as well as peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, and tert-butylperoxypivalate.

[0077] The amount of the polymerization initiator used is generally preferably 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, and is preferably 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, relative to 100 parts by mass of the total of the polymerizable monomers.

[0078] 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, dithiocarbamate, trithiocarbonate, or xanthate.

[0079] The RAFT agent can be used in the range of 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the total amount of polymerizable monomers.

[0080] The weight-average molecular weight (Mw) of the first resin (D) can be 3,000 to 80,000, preferably 4,000 to 70,000, and more preferably 5,000 to 60,000. The number-average molecular weight (Mn) can be 1,000 to 30,000, preferably 1,500 to 25,000, and more preferably 2,000 to 20,000. The polydispersity (Mw / Mn) can be 1.0 to 3.5, preferably 1.1 to 3.0, and more preferably 1.2 to 2.8. By setting the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (Mw / Mn) within the above ranges, a positive-type photosensitive resin composition with excellent alkali solubility and developability can be obtained.

[0081] The first resin (D) may have some of its phenolic hydroxyl groups protected with acid-decomposable groups. Resins in which some of their phenolic hydroxyl groups are protected with acid-decomposable groups have reduced alkali solubility before exposure. By optionally performing post-exposure baking (PEB) in the presence of acid generated during exposure, decomposition (deprotection) of the acid-decomposable groups is promoted, and alkali-soluble functional groups are regenerated. This promotes alkali dissolution of the binder resin (A) in the exposed areas during development. The binder resin (A) may contain one type or a combination of two or more types. For example, the binder resin (A) may contain two or more types of resins that differ in the polymer structural unit, acid-decomposable group, protection rate of alkali-soluble functional group, or combination thereof.

[0082] 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; X R Y -OR Z (In the formula, R X and R Y are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R Z is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, or R X or R Y One of the two and R Z and may be bonded to form a ring structure having 3 to 10 ring members. X R Y -OR Z The group represented by the formula (I) forms an acetal structure or a ketal structure together with the oxygen atom derived from the phenolic hydroxyl group. These acid-decomposable groups can be used alone or in combination of two or more.

[0083] Since a positive photosensitive resin composition having high sensitivity can be obtained even with a low exposure dose, the acid-decomposable group is a group represented by the formula: -CR X R Y -OR Zand more preferably a 1-alkoxyalkyl group. Examples of the 1-alkoxyalkyl group include a methoxymethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a 1-(2-chloroethoxy)ethyl group, a 1-(2-ethylhexyloxy)ethyl group, a 1-cyclohexyloxyethyl group, and a 1-(2-cyclohexylethoxy)ethyl group, with a 1-ethoxyethyl group and a 1-n-propoxyethyl group being preferred.

[0084] As the acid-decomposable group, a group of the formula: -CR X R Y -OR Z is a group represented by R X or R Y One of the two and R Z and R bonded to form a ring structure having 3 to 10 ring members can also be suitably used. In this case, R not involved in the formation of the ring structure can be used. X or R Y is preferably a hydrogen atom. Examples of such an acid-decomposable group include a 2-tetrahydropyranyl group and a 2-tetrahydrofuranyl group.

[0085] In one embodiment, the positive photosensitive resin composition contains 5% to 75% by mass, preferably 10% to 60% by mass, and more preferably 15% to 45% by mass of the first resin (D) based on 100% by mass of the solid content. When the content of the first resin (D) is 5% by mass or more based on 100% by mass of the solid content, a pattern can be formed with good resolution. When the content of the first resin (D) is 75% by mass or less based on 100% by mass of the solid content, the solubility of the unexposed area can be kept low, and a high residual film rate can be maintained.

[0086] [Second resin (E) having epoxy groups and phenolic hydroxyl groups] The second resin (E) having an epoxy group and a phenolic hydroxyl group is an alkaline aqueous solution-soluble resin. The second resin (E) may have an alkali-soluble functional group other than a phenolic hydroxyl group. The phenolic hydroxyl group and other alkali-soluble functional groups may be protected with an acid-decomposable group. The second resin (E) can be obtained, for example, by reacting the epoxy group of a compound having at least two epoxy groups per molecule (hereinafter sometimes referred to as an "epoxy compound") with the carboxy group of a hydroxybenzoic acid compound. The epoxy group in the second resin (E) forms a crosslink by reaction with the phenolic hydroxyl group during post-development heat treatment (post-bake), thereby improving the chemical resistance and heat resistance of the coating. Since the phenolic hydroxyl group contributes to solubility in an alkaline aqueous solution during development, the second resin (E) also functions as a dissolution promoter, thereby improving the sensitivity of the photosensitive resin composition.

[0087] The following reaction formula 1 shows an example of a reaction in which one of the epoxy groups of an epoxy compound reacts with the carboxy group of a hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group. [ka]

[0088] Examples of compounds having at least two epoxy groups per molecule include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol epoxy resins, biphenol epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds may contain two or more epoxy groups per molecule, and may be used alone or in combination of two or more. Because these compounds are thermosetting, it is common knowledge among those skilled in the art that their structures cannot be unambiguously described due to differences in the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, and the like.

[0089] An example of the structure of a novolac epoxy resin is shown in formula (4). In formula (4), for example, R 9 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a hydroxyl group; and m is an integer of 1 to 50. [ka]

[0090] Examples of phenol novolac epoxy resins include EPICLON (registered trademark) N-770 (DIC Corporation) and jER (registered trademark)-152 (Mitsubishi Chemical Corporation). Examples of cresol novolac epoxy resins include EPICLON (registered trademark) N-695 (DIC Corporation) and EOCN (registered trademark)-102S (Nippon Kayaku Co., Ltd.). Examples of bisphenol epoxy resins include bisphenol A epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (Mitsubishi Chemical Corporation), and YD-128 (trade name, Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F epoxy resins such as jER (registered trademark) 806 (Mitsubishi Chemical Corporation) and YDF-170 (trade name, Nippon Steel Chemical & Material Co., Ltd.). Examples of biphenol-type epoxy resins include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include NC-7000 (trade name, Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, DIC Corporation). Examples of alicyclic epoxy resins include EHPE (registered trademark)-3150 (Daicel Chemical Industries, Ltd.). Examples of heterocyclic epoxy resins include TEPIC (registered trademark), TEPIC-L, TEPIC-H, and TEPIC-S (Nissan Chemical Industries, Ltd.).

[0091] 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 (E) derived from a novolac epoxy resin has excellent pattern formability, easy adjustment of alkali solubility, and little outgassing.

[0092] The hydroxybenzoic acid compound is a compound in which at least one of the 2- to 6-positions of benzoic acid is substituted with a hydroxyl group, and examples thereof include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, and 4-hydroxy-3-nitrobenzoic acid. Dihydroxybenzoic acid compounds are preferred in terms of enhancing alkaline developability. One type of hydroxybenzoic acid compound may be used alone, or two or more types may be used in combination.

[0093] In one embodiment, the second resin (E) having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid compound, and is represented by the formula (3): [ka] In formula (3), 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.

[0094] In the method of obtaining the second resin (E) 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 hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if it is 1.0 equivalent or less, an increase in molecular weight due to side reactions can be suppressed.

[0095] In the method for obtaining the second resin (E) from an epoxy compound and a hydroxybenzoic acid compound, a catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of catalyst used may be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture consisting of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature may be 60 to 150°C, and the reaction time may be 3 to 30 hours.

[0096] Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octoate, and zirconium octoate.

[0097] The number average molecular weight (Mn) of the second resin (E) having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and even more preferably 1000 to 5000. If the number average molecular weight is 500 or more, the resin has suitable alkali solubility and is therefore suitable as a resin for photosensitive materials, and if it is 8000 or less, the resin has good coatability and developability.

[0098] In one embodiment, the epoxy equivalent of the second resin (E) having an epoxy group and a phenolic hydroxyl group is 300 to 7000, preferably 400 to 6000, and more preferably 500 to 5000. When the epoxy equivalent of the second resin (E) is 300 or more, the resin having an epoxy group and a phenolic hydroxyl group can exhibit sufficient alkali solubility. When the epoxy equivalent of the second resin (E) is 7000 or less, the coating strength and heat resistance after curing can be improved. The epoxy equivalent is determined according to JIS K 7236:2009.

[0099] In one embodiment, the hydroxyl equivalent of the second resin (E) having an epoxy group and a phenolic hydroxyl group is 160 to 500, preferably 170 to 400, and more preferably 180 to 300. If the hydroxyl equivalent of the second resin (E) is 160 or more, the strength and heat resistance of the cured coating can be improved. If the hydroxyl equivalent of the second resin (E) is 500 or less, the resin having an epoxy group and a phenolic hydroxyl group can exhibit sufficient alkali solubility. The hydroxyl equivalent is determined according to JIS K 0070:1992.

[0100] In one embodiment, the positive photosensitive resin composition contains 5% to 50% by mass, preferably 10% to 40% by mass, and more preferably 15% to 30% by mass of the second resin (E) based on 100% by mass of the solids content. When the content of the second resin (E) is 5% by mass or more based on 100% by mass of the solids content, dissolution of the exposed area can be promoted, achieving high sensitivity and ensuring the stability and durability of the coating after thermal curing. When the content of the second resin (E) is 50% by mass or less based on 100% by mass of the solids content, the solubility of the unexposed area can be kept low, maintaining a high film residual rate.

[0101] <Photoacid generator (B)> The positive-type photosensitive resin composition contains a photoacid generator (B). The photoacid generator (B) is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, gamma rays, or electron beams. The presence of the acid generated by the photoacid generator (B) in the irradiated area makes the resin in that area more soluble in an alkaline aqueous solution together with the acid. When the binder resin (A) contains an alkali-soluble functional group, some of which is protected with an acid-decomposable group, the photoacid generator (B) promotes decomposition of the acid-decomposable group to regenerate the alkali-soluble functional group, thereby increasing the alkali solubility of the binder resin (A). Therefore, by including the photoacid generator (B) in the positive-type photosensitive resin composition, it is possible to form a high-resolution pattern with high sensitivity even at a low exposure dose.

[0102] As the photoacid generator (B), it is preferable to use at least one selected from the group consisting of quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. The photoacid generator (B) can be used alone or in combination of two or more kinds.

[0103] In one embodiment, the positive photosensitive resin composition contains 5 to 70 parts by mass, preferably 10 to 65 parts by mass, and more preferably 13 to 60 parts by mass of the photoacid generator (B) based on a total of 100 parts by mass of the resin components. When the content of the photoacid generator (B) is 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 (B) is 70 parts by mass or less based on the total of 100 parts by mass, alkaline developability is good.

[0104] The positive-type photosensitive resin composition preferably uses a quinone diazide compound as the photoacid generator (B). When irradiated with radiation such as visible light, ultraviolet light, gamma rays, or electron beams, the quinone diazide compound generates an alkali-soluble carboxylic acid compound via the reaction shown in Reaction Scheme 2 below. Before exposure, the quinone diazide compound interacts (e.g., forms hydrogen bonds) with functional groups of the binder resin (A) such as a novolac resin, rendering the binder resin (A) insoluble in an alkaline aqueous solution. Meanwhile, the presence of the alkali-soluble carboxylic acid compound in the irradiated area facilitates the dissolution of the resin in that area together with the carboxylic acid compound in an alkaline aqueous solution. Furthermore, the carboxylic acid compound has a relatively larger molecular structure than acids generated by photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is therefore less likely to diffuse within the film. These synergistic effects result in a greater difference in alkali solubility between the unexposed and exposed areas, enabling the formation of high-sensitivity, high-resolution patterns even at low exposure doses. The quinone diazide compounds can be used alone or in combination of two or more.

[0105] [ka]

[0106] In one embodiment, high-resolution patterns can be formed without the post-exposure bake (PEB) required for typical chemically amplified resists. The quinone diazide compound has a relatively high quantum yield, allowing efficient production of carboxylic acid compounds in exposed areas. By omitting PEB, it is possible to suppress deterioration in pattern formability due to excessive diffusion of the acid generated from the photoacid generator to unexposed areas in the high-temperature environment of PEB. Furthermore, when using a second resin (E) having epoxy groups and phenolic hydroxyl groups, omitting PEB prevents ring-opening polymerization of the epoxy groups in the second resin (E) having epoxy groups and phenolic hydroxyl groups, thereby maintaining the alkali solubility of the second resin (E) having epoxy groups and phenolic hydroxyl groups during development.

[0107] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond or a sulfonamide bond. From the viewpoint of contrast between exposed and unexposed areas, it is preferred that 20 mol % or more of the total functional groups of the polyhydroxy compound or polyamino compound be substituted with quinone diazide.

[0108] Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Tyrol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TM Examples of suitable phenols include, but are not limited to, L-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all trade names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (all trade names, Asahi Organic Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.).

[0109] Examples of polyamino compounds include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0110] Polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

[0111] 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.

[0112] In one embodiment, the positive photosensitive resin composition contains a quinone diazide compound in an amount of 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass, and more preferably 8% by mass to 35% by mass, based on 100% by mass of the solid content. When the content of the quinone diazide compound is 1% by mass or more, based on 100% by mass of the solid content, high sensitivity can be achieved. When the content of the quinone diazide compound is 50% by mass or less, based on 100% by mass of the solid content, good alkaline developability can be achieved.

[0113] The positive photosensitive resin composition may use an oxime sulfonate compound as the photoacid generator (B). Examples of the oxime sulfonate compound include compounds represented by formula (6). [ka]

[0114] In equation (6), R 10 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom; R11 and R 12 R are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, an acyloxy group, a carboxy group, an alkoxycarbonyl group, or a fluoroalkyl group. 11 and R 12 may be bonded to form a ring structure. The ring structure preferably has 3 to 10 ring members.

[0115] R 10 Examples of the substituted or unsubstituted alkyl group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms, and a methyl group, an ethyl group, or an n-propyl group is preferred.

[0116] R 10 The substituted or unsubstituted alkoxy group includes, for example, a linear alkoxy group having 1 to 5 carbon atoms or a branched alkoxy group having 3 to 5 carbon atoms, and is preferably a methoxy group or an ethoxy group.

[0117] R 10 Examples of the substituents on the alkyl and alkoxy groups include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), cyano groups, nitro groups, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms.

[0118] R 10 The alkyl group of the substituent is preferably a fluoroalkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group, and even more preferably a trifluoromethyl group.

[0119] R 10 The substituted or unsubstituted aryl group includes, for example, an aryl group having 6 to 20 carbon atoms, and is preferably a phenyl group, a 4-methylphenyl group, or a naphthyl group.

[0120] R 10Examples of the substituent on the aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

[0121] R 10 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0122] 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 12 Examples of the substituted or unsubstituted heterocyclic group include a 2-benzofuranyl group, a 3-benzofuranyl group, a 2-benzimidazolyl group, a 2-benzoxazolyl group, a 2-benzothiazolyl group, a 2-indolyl group, a 3-coumarinyl group, a 4-coumarinyl group, a 3-isocoumarinyl group, and a 4-isocoumarinyl group.

[0123] R 11 and R 12 Examples of the substituents on the aryl group and heterocyclic group include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acyloxy groups having 2 to 4 carbon atoms, and halogen atoms (fluorine atom, chlorine atom, bromine atom, and iodine atom).

[0124] R 11 and R 12 Examples of the acyloxy group of R include an acetoxy group and a benzoyl group. 11 and R 12 The alkoxycarbonyl group includes, for example, an ethoxycarbonyl group.

[0125] R 11 and R 12 Examples of the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.

[0126] R 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.

[0127] R 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.

[0128] R 11 and R 12 Examples of the oxime sulfonate compound having a ring structure formed by bonding the above 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.

[0129] <At least one colorant (F) selected from the group consisting of black dyes and black pigments> The colorant (F) 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, by forming black partition walls in an organic EL element using a positive photosensitive resin composition containing the colorant (F), the visibility of a display device such as an organic EL display can be improved.

[0130] In one embodiment, the colorant (F) comprises a black dye. A dye defined by a color index (CI) of Solvent Black 27 to 47 can be used as the black dye. The black dye is preferably defined by a CI of Solvent Black 27, 29, or 34. When at least one of the dyes defined by a CI of Solvent Black 27 to 47 is used as the black dye, the light-blocking properties of the film of the positive photosensitive resin composition after baking can be maintained. A positive photosensitive resin composition containing a black dye leaves less residue of the colorant (F) during development than a positive photosensitive resin composition containing a black pigment, and a high-resolution pattern can be formed in the film.

[0131] A black pigment may be used as the colorant (F). 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 versions of these black pigments can also be used.

[0132] Examples of commercially available perylene pigments include BASF's K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34. Examples of commercially available lactam pigments include BASF's Irgaphor® Black S0100CF.

[0133] The black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene pigments, and lactam pigments, as these have high light-blocking properties.

[0134] In one embodiment, the positive photosensitive resin composition contains 10 to 150 parts by mass of colorant (F), preferably 20 to 100 parts by mass, and more preferably 30 to 70 parts by mass, based on 100 parts by mass of the total resin components. When the content of colorant (F) is 10 parts by mass or more based on the total 100 parts by mass, the light-blocking properties of the coating film after baking can be maintained. When the content of colorant (F) is 150 parts by mass or less based on the total 100 parts by mass, the coating film can be colored without impairing alkaline developability.

[0135] <Dissolution promoter (G)> The positive photosensitive resin composition may further contain a dissolution promoter (G) for improving the solubility of the alkali-soluble portion in the developer during development.

[0136] The dissolution promoter (G) may be an organic low molecular weight compound selected from the group consisting of compounds having a carboxy group and compounds having a phenolic hydroxyl group. The dissolution promoter (G) may be used alone or in combination of two or more.

[0137] 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.

[0138] Examples of such organic low molecular weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; and aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimellitic acid, and mesitylene acid. aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, and pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umbellic acid; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

[0139] The content of the dissolution promoter (G) 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 resin components. If the content of the dissolution promoter (G) is 0.1 part by mass or more based on the total 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.

[0140] <Optional component (H)> The positive photosensitive resin composition may contain, as an optional component (H), a heat curing agent, a surfactant, a colorant other than the colorant (F), etc. In the present disclosure, the optional component (H) is defined as any component other than the binder resin (A) (the first resin (D), the second resin (E), and other resins), the photoacid generator (B), the solvent (C), the colorant (F), and the dissolution promoter (G).

[0141] The photosensitive resin composition may contain a basic compound as an optional component (H) to ensure the long-term reliability of the organic EL device. The basic compound acts as a quencher for acidic components or acidic sites, such as carboxylic acids and phenolic hydroxyl groups, contained in the photosensitive resin composition, or for acidic gases generated from photoacid generators. When the coating is used in an organic EL device, the use of a basic compound can prevent a decrease in luminance, pixel shrinkage, the occurrence of dark spots, and other problems.

[0142] Examples of basic compounds include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, 3-(2-ethylhexyloxy)propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, N-ethylamine, tri-n-nonylamine, tri-n-decylamine, tricyclohexylamine, triphenylamine, aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'- Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene, imidazole, benzimidazole, 4-methylimidazoline azole, 4-methyl-2-phenylimidazole, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, quinoline, 8-oxyquinoline, acridine, pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, and 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine.

[0143] The content of the basic compound is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, based on 100 parts by mass of the total solid content excluding the basic compound.

[0144] A thermal radical generator can be used as the thermal curing agent. Preferred examples of the thermal radical generator include organic peroxides, specifically organic peroxides having a 10-hour half-life temperature of 100 to 170°C, such as dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

[0145] The content of the heat curing agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the heat curing agent.

[0146] 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.

[0147] Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafac (registered trademark) F-251 and 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 AGC Seimi Chemical Co., Ltd.), and organosiloxane polymers KP323, KP326, and KP341 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more.

[0148] 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.

[0149] The positive photosensitive resin composition may contain at least one second colorant other than the colorant (F) selected from the group consisting of black dyes and black pigments. Examples of the second colorant include dyes, organic pigments, and inorganic pigments, and can be used according to the purpose. The second colorant can be used in an amount that does not impair the effects of the present disclosure.

[0150] 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.

[0151] 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, CI Pigment Brown 23, 25, 26, and the like.

[0152] The positive photosensitive resin composition can be prepared by dissolving or dispersing the binder resin (A), the photoacid generator (B), and, if necessary, the colorant (F), the dissolution promoter (G), or the optional component (H) in a solvent (C) containing the components (c1) to (c3) and mixing them. The solids concentration of the positive photosensitive resin composition can be appropriately determined depending on the intended use. For example, the solids concentration of the positive photosensitive resin composition may be 1 to 60 mass %, 3 to 50 mass %, or 5 to 40 mass %.

[0153] When using a pigment, any known method can be used for dispersion and mixing. For example, ball-type devices such as a ball mill, sand mill, bead mill, paint shaker, and rocking mill, blade-type devices such as a kneader, paddle mixer, planetary mixer, and Henschel mixer, and roll-type devices such as a three-roll mixer, as well as Raikai mixers, colloid mills, ultrasonic devices, homogenizers, and rotation-revolution mixers may be used. The use of a bead mill is preferred from the viewpoint of dispersion efficiency and fine dispersion.

[0154] The prepared positive photosensitive resin composition is usually filtered before use, for example, using a Millipore filter with a pore size of 0.05 to 1.0 μm.

[0155] <Method of using the positive photosensitive resin composition> When a positive-type photosensitive resin composition is used in radiation lithography, a coating composition is first prepared by dissolving or dispersing the positive-type photosensitive resin composition in a solvent. The coating composition is then applied to a substrate surface, and the solvent is removed by heating or other means to form a coating film. The method for applying the coating composition to the substrate surface is not particularly limited, and examples of methods that can be used include spraying, roll coating, slit coating, and spin coating.

[0156] After applying the coating composition to the surface of a substrate, the solvent is usually removed by heating to form a coating (pre-baking). The heating conditions vary depending on the type and blending ratio of each component, but the coating can usually be obtained by heating at 70 to 130°C for 30 seconds to 20 minutes on a hot plate or 1 to 60 minutes in an oven.

[0157] Next, the prebaked coating is irradiated with radiation (e.g., 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 (B), preferred radiation is ultraviolet light or visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-ray. In another embodiment, the radiation is ghi-ray.

[0158] 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 (B). When the binder resin (A) of the positive photosensitive resin composition has a protected alkali-soluble functional group, PEB promotes deprotection of the protected alkali-soluble functional group in the exposed area, thereby further increasing the alkali solubility of the binder resin (A). 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, for example, 30 seconds to 20 minutes on a hot plate or 1 to 60 minutes in an oven. In one embodiment, PEB after the exposure step can be omitted.

[0159] After the exposure step or PEB step, the coating is developed by contacting it with a developer to remove unnecessary portions and form a pattern in the coating (development step). Examples of the developer include aqueous solutions of alkaline compounds such as inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; 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. Aqueous solutions prepared by adding appropriate amounts of water-soluble organic solvents such as methanol and ethanol, surfactants, etc. to an alkaline aqueous solution can also be used as the developer.

[0160] The development time is usually 30 to 180 seconds. The development method may be any of the puddle method, shower method, or dipping method. After development, the film is washed with running water for 30 to 90 seconds to remove unnecessary portions, and then air-dried with compressed air or compressed nitrogen, thereby forming a pattern in the film.

[0161] Thereafter, the coating film on which the pattern has been formed is heat-treated, for example, at 100 to 350°C for 20 to 200 minutes using a heating device such as a hot plate or oven, to obtain a cured coating film (post-baking, heat treatment step). In the heat treatment, the temperature may be maintained constant, or may be increased continuously or stepwise. The heat treatment is preferably carried out in a nitrogen atmosphere.

[0162] 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 0.6 or more, and even more preferably 0.7 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.

[0163] In one embodiment, a method for producing an organic EL device partition wall or insulating film includes dissolving or dispersing a positive photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a coating film, removing the solvent contained in the coating and drying the coating, exposing the dried coating to radiation through a photomask, developing the exposed coating by contacting it with a developer to form a pattern in the coating, and heat-treating the patterned coating at a temperature of 100° C. to 350° C. to form an organic EL device partition wall or insulating film. The PEB described above can also be performed after exposure and before development.

[0164] One embodiment is a partition wall for an organic EL device, which comprises a cured product of a positive-type photosensitive resin composition.

[0165] One embodiment is an insulating film for an organic EL device, which comprises a cured product of a positive photosensitive resin composition.

[0166] One embodiment is an organic EL device containing a cured product of the positive photosensitive resin composition. [Example]

[0167] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

[0168] (1) Raw materials The raw materials used in the examples and comparative examples were produced or obtained as follows.

[0169] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the binder resin (A) were calculated using a calibration curve prepared using a polystyrene standard substance under the following measurement conditions. Equipment: Shodex® GPC-101 Column: Shodex (registered trademark) LF-804 Mobile phase: tetrahydrofuran Flow rate: 1.0mL / min Detector: Shodex (registered trademark) RI-71 Temperature: 40℃

[0170] <Solvent (C)> [Examples 1 to 6, Comparative Examples 1 to 6] In Examples 1 to 6 and Comparative Examples 1 to 6, the following solvents were used as mixed solvents in the proportions shown in Table 1. The proportion of each solvent in Table 1 is expressed as mass % relative to the total amount of solvent. (c1) γ-butyrolactone (GBL) (Mitsubishi Chemical Corporation) (c2) 1-Methoxy-2-propyl acetate (PGMEA) (Daicel Corporation) (c3) Acetate ester n-Butyl acetate (n-BuOAc) (Kanto Chemical Co., Ltd., special grade) i-Butyl acetate (i-BuOAc) (Kanto Chemical Co., Ltd., special grade) n-Pentyl acetate (n-PentOAc) (Kanto Chemical Co., Ltd., special grade) i-Propyl acetate (i-PrOAc) (Kanto Chemical Co., Ltd., special grade) Ethyl acetate (EtOAc) (Junsei Chemical Co., Ltd., special grade) Allyl acetate (AllylOAc) (Showa Denko K.K.) (others) Ethyl lactate (EL) (Musashino Chemical Laboratory Co., Ltd.) Diethyl carbonate (DEC) (Tokyo Chemical Industry Co., Ltd.) 1-Methoxy-2-propanol (PGME) (Daicel Corporation)

[0171] [Examples 7 to 15] In Examples 7 to 15, the above (c1) GBL, (c2) PGMEA, and (c3) i-BuOAc were used, and the following solvents were further used to form mixed solvents in the proportions shown in Table 2. The proportions of each solvent in Table 2 are in mass % relative to the total amount of solvent. (c4) Amide compounds 1-Methyl-2-pyrrolidone (NMP) (Kanto Chemical Co., Ltd., special grade) 1,3-Dimethyl-2-imidazolidinone (DMI) (Kanto Chemical Co., Ltd., special grade) 3-Methyl-2-oxazolidone (MOX) (Tokyo Chemical Industry Co., Ltd.) 3-Methoxy-N,N-dimethylpropionamide (MDPA) (Tokyo Chemical Industry Co., Ltd.) 1-Cyclohexyl-2-pyrrolidone (NCP) (Tokyo Chemical Industry Co., Ltd.) (others) Propylene carbonate (PC) (Kanto Chemical Co., Ltd., special grade) Diethylene glycol monoethyl ether acetate (EDGAC) (Kanto Chemical Co., Ltd., special grade) Diethylene glycol mono-n-butyl ether acetate (BDGAC) (Kanto Chemical Co., Ltd., special grade)

[0172] [Production Example 1] Production of first resin (D) (PCX-02e) having multiple phenolic hydroxyl groups 25.5 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA") and 4.50 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (Daicel Corporation). The two resulting solutions were simultaneously added dropwise over 2 hours to 61.2 g of 1-methoxy-2-propyl acetate (Daicel Corporation) heated to 85 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask, and then reacted at 85 °C for 3 hours. The reaction solution was cooled to room temperature and added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 90°C for 4 hours, and 32.4 g of white powder (PCX-02e) was collected. The number-average molecular weight of the obtained PCX-02e was 3,100 and the weight-average molecular weight was 6,600.

[0173] [Production Example 2] Production of second resin (E) (N695OH70) having epoxy groups and phenolic hydroxyl groups A 300 mL three-neck flask was charged with 75.2 g of 1-methoxy-2-propyl acetate (MMPGAC, Daicel Corporation) as a solvent and 17.8 g of EPICLON® N-695 (DIC Corporation, cresol novolac epoxy resin, epoxy equivalent weight 214) as a compound having at least two epoxy groups per molecule, and dissolved under a nitrogen gas atmosphere at 60 °C. 20.1 g (0.65 equivalents per epoxy equivalent) of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound and 0.166 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added, and the mixture was reacted at 110 °C for 21 hours. The reaction solution was returned to room temperature, diluted with 1-methoxy-2-propyl acetate to a solids content of 20% by mass, and filtered to obtain 274.2 g of a solution of a second resin (N695OH70) having epoxy groups and phenolic hydroxyl groups. The resulting reaction product (N695OH70) had a number average molecular weight of 3,000 and a weight average molecular weight of 7,500.

[0174] <Binder resin (A)> As the binder resin (A), PCX-02e (first resin (D)) obtained in Production Example 1, N695OH70 (second resin (E)) obtained in Production Example 2, and EPICLON (registered trademark) N-695 (DIC Corporation, cresol novolac epoxy resin, epoxy equivalent 214) (other resin) were used.

[0175] <Photoacid generator (B)> As the photoacid generator (B), TPPA-150DF (Toyo Gosei Co., Ltd., 1,2-naphthoquinone diazide-4-sulfonic acid ester of α,α,α-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene) was used.

[0176] <Colorant (F)> As the colorant (F), a black dye, VALIFAST (registered trademark) BLACK 3804 (a black dye specified by the CI of Solvent Black 34, Orient Chemical Industries Co., Ltd.) was used.

[0177] <Dissolution promoter (G)> Phloroglucinol (Fujifilm Wako Chemical Co., Ltd.) was used as the dissolution promoter (G).

[0178] <Other ingredients> As optional component (H), a surfactant (leveling agent) Megafac (registered trademark) F-559 (fluorine-based surfactant, DIC Corporation) and a basic compound trioctylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) were used.

[0179] (2) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[0180] [Solubility of unexposed areas] A positive photosensitive resin composition was bar-coated onto a glass substrate (72 mm x 72 mm x 0.7 mm) to a dry film thickness of 4.0 μm. The substrate was placed in a vacuum chute (VKU-100, Kiriyama Seisakusho Co., Ltd.) and vacuum-dried for 30 seconds using an air-cooled dry pump (PK-250, Yamato Scientific Co., Ltd.). The solvent was then dried by heating on a hot plate at 125°C for 2 minutes. The dry film thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.).

[0181] Next, using a spin developer (AD-1200, Takizawa Sangyo Co., Ltd.), alkaline development was performed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 to 100 seconds, so that the solubility of the unexposed area was between 0.35 μm and 0.99 μm. The film thickness after alkaline development was measured again using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.), and the difference in film thickness before and after development (film thickness dissolved by development) (μm) was calculated as the solubility of the unexposed area.

[0182] [Solubility of exposed areas] (Examples 1 to 6, Comparative Examples 1 to 6) A positive photosensitive resin composition was bar-coated onto a glass substrate (72 mm x 72 mm x 0.7 mm) to a dry film thickness of 4.0 μm. The substrate was placed in a vacuum chute (VKU-100, Kiriyama Seisakusho Co., Ltd.) and vacuum-dried for 30 seconds using an air-cooled dry pump (PK-250, Yamato Scientific Co., Ltd.). The substrate was then pre-baked by heating on a hot plate at 125°C for 2 minutes. The dry film thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.).

[0183] Next, using an exposure device (product name: Multilight ML-251A / B, Ushio Inc.) equipped with an ultra-high pressure mercury lamp, the ghi line was irradiated at 300 mJ / cm through 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 dose was measured using an ultraviolet integrating actinometer (product name: UIT-150, light receiving part: UVD-S365, Ushio Inc.).

[0184] After exposure, alkaline development was performed using a spin developer (AD-1200, Takizawa Sangyo Co., Ltd.) with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for the same development time as in the evaluation of the solubility of the unexposed area. The film thickness after alkaline development was measured again using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.), and the difference in film thickness before and after development (film thickness dissolved by development) (μm) was calculated as the solubility of the exposed area.

[0185] (Examples 7 to 15) In the evaluation of the solubility of the exposed area carried out in the above-mentioned Examples 1 to 6 and Comparative Examples 1 to 6, an exposure apparatus incorporating an ultra-high pressure mercury lamp (product name: Multilight ML-251A / B, Ushio Inc.) was used, and only i-line was irradiated at 400 mJ / cm through a mercury exposure bandpass filter (product name: HB0365, Asahi Spectroscopy 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). 2The solubility of the exposed area was calculated in the same manner except that the exposure was carried out at 1000 kJ / min.

[0186] [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 indicates higher sensitivity and superior pattern formability. For Examples 1 to 6 and Comparative Examples 1 to 6, a solubility difference of 3.30 μm or more was evaluated as good, and one less than 3.30 μm was evaluated as poor. For Examples 7 to 15, a solubility difference of 3.20 μm or more was evaluated as very good, one between 2.90 μm and 3.20 μm was evaluated as good, and one less than 2.90 μm was evaluated as poor.

[0187] [Pinmura Rating] A glass substrate (72 mm × 72 mm × 0.7 mm) was bar-coated with a positive photosensitive resin composition to a dry film thickness of 4.0 μm. Proximity pins (made of stainless steel, 1 cm diameter, 1 mm thick) were placed on a hot plate at 125°C, and the substrate was pre-baked by heating for 2 minutes. The film thicknesses of the areas that were on the proximity pins and the areas that were not on the proximity pins during heating were measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.), and the difference was calculated. Evaluation was performed with a difference of less than 1.6 μm as good, a difference of 1.6 μm to 2.0 μm as passable, and a difference of 2.0 μm or more as poor.

[0188] [OD value of cured film] A positive photosensitive resin composition was bar-coated onto a glass substrate (70 mm × 70 mm × 0.7 mm) to a dry film thickness of approximately 1.5 μm, and the coating was heated on a hot plate at 125°C for 2 minutes to evaporate the solvent. The coating was then cured at 250°C for 60 minutes in a nitrogen gas atmosphere to obtain a coating. The OD value of the cured coating was measured using a transmission densitometer (BMT-1, Sakata Inx Engineering Co., Ltd.), corrected for the OD value of the glass alone, and converted to an OD value per 1 μm of coating thickness. The coating thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.).

[0189] (3) Preparation and evaluation of positive photosensitive resin compositions [Examples 1 to 15, Comparative Examples 1 to 6] The binder resin (A) was mixed and dissolved in the composition shown in Table 3. To the resulting solution, the photoacid generator (B), colorant (F), dissolution promoter (G), optional component (H) (surfactant and basic compound) shown in Table 3, and mixed solvent (C) shown in Table 1 or Table 2 were added and further mixed. After visually confirming that the components had dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solids concentration of 12 mass %. The parts by mass of the composition in Table 3 are values ​​calculated as solids. The evaluation results of the positive photosensitive resin compositions of Examples 1 to 15 and Comparative Examples 1 to 6 are shown in Tables 1 and 2.

[0190] [Table 1]

[0191] [Table 2]

[0192] [Table 3]

Claims

1. A binder resin (A), a photoacid generator (B); a solvent (C); at least one colorant (F) selected from the group consisting of black dyes and black pigments; A positive photosensitive resin composition comprising the solvent (C): (c1) γ-butyrolactone, (c2) 1-methoxy-2-propyl acetate, and (c3) Acetate ester represented by the following formula (7): 【Chemistry 1】 (In formula (7), R ５ represents a hydrocarbon group having 1 to 12 carbon atoms. Including, the binder resin (A) contains a first resin (D) having a plurality of phenolic hydroxyl groups, The first resin (D) is represented by the formula (1) 【Chemistry 2】 (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) 【Transformation 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 fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R ４ is a phenyl group substituted with at least one selected from the group consisting of a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. and a structural unit represented by the photoacid generator (B) contains a quinone diazide compound, the binder resin (A) further contains a second resin (E) having an epoxy group and a phenolic hydroxyl group, The second resin (E) is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid compound, and is represented by the formula (3): 【Chemistry 4】 (In formula (3), 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 epoxy resin, The hydroxybenzoic acid compound is a dihydroxybenzoic acid compound. A positive photosensitive resin composition.

2. 2. The positive photosensitive resin composition according to claim 1, wherein the (c3) acetate ester is at least one selected from the group consisting of n-butyl acetate and i-butyl acetate.

3. 3. The positive photosensitive resin composition according to claim 1, wherein the content of (c1) γ-butyrolactone is 10% by mass to 60% by mass, the content of (c2) 1-methoxy-2-propyl acetate is 20% by mass to 80% by mass, and the content of (c3) acetic acid ester is 5% by mass to 40% by mass, relative to 100% by mass of the solvent (C).

4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the solvent (C) further contains at least one amide compound (c4) selected from the group consisting of formulas (8), (9), and (10): 【Transformation 5】 (In formula (8), R ａ is a hydrocarbon group having 1 to 8 carbon atoms, which may have an alkoxy group having 1 to 6 carbon atoms as a substituent, and R ｂ and R ｃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ａ , R ｂ , and R ｃ may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent. 【Transformation 6】 (In formula (9), R ｄ is a hydrocarbon group having 1 to 6 carbon atoms, and R ｅ and R ｆ are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ｄ , R ｅ , and R ｆ may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent. 【Transformation 7】 (In formula (10), R ｇ , R ｈ , R ｉ , and R ｊ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ｇ , R ｈ , R ｉ , and R ｊ may be bonded in any combination to form a ring structure which may have an alkyl group having 1 to 6 carbon atoms as a substituent.

5. 5. The positive photosensitive resin composition according to claim 4, wherein the content of the amide compound (c4) is 0.01% by mass to 10% by mass relative to 100% by mass of the solvent (C).

6. 2. 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.

7. A partition wall for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 6.

8. An insulating film for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 6.

9. An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 6.

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