Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device

Abstract

To provide a photosensitive resin composition that can reduce fume emission during firing.SOLUTION: A photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound. The alkali-soluble resin (A) includes an alkali-soluble resin (A1), which is a reaction product of component (a1) and component (a2), component (a3), and component (a4). The component (a1) is at least one selected from the group consisting of epoxy compounds represented by the following formula (1) and the like. The component (a2) is at least one selected from the group consisting of α,β-unsaturated monocarboxylic acids and α,β-unsaturated monocarboxylic acid esters having a carboxyl group. The component (a3) is at least one selected from the group consisting of tricarboxylic acids and anhydrides thereof. The component (a4) is at least one selected from the group consisting of tetracarboxylic acids and anhydrides thereof.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product, a partition wall, an organic electroluminescent element, a color filter, and an image display device.

Background Art

[0002] A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage applied to the liquid crystal. Many of the members constituting the cell of the LCD are formed by a method using a photosensitive composition, typified by the photolithography method. This photosensitive composition is easy to form a fine structure and easy to process a large-screen substrate, and thus its application range is further expanding.

[0003] An image display device including an organic electroluminescent element (also referred to as organic electroluminescence or organic EL) attracts attention as a next-generation flat panel display (FPD) because it has excellent visibility and responsiveness such as contrast and viewing angle, can reduce power consumption, is thin and lightweight, and can make the display body flexible. An organic electroluminescent element has a structure in which an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes at least one of which has translucency. The image display device performs image display by driving a panel in which organic electroluminescent elements are arranged for each pixel. Conventionally, such an organic electroluminescent element has been manufactured by forming a partition wall (bank) on a substrate and then laminating a light-emitting layer or various functional layers in a region surrounded by the partition wall.

[0004] To form a light-emitting layer or the like within a region surrounded by partitions, a vapor deposition method is mainly applied, in which the material is sublimated in a vacuum state and deposited on a substrate to form a film. In recent years, methods of forming a film by wet processes such as a casting method, a spin coating method, and an inkjet printing method have attracted attention. In particular, the inkjet printing method can reduce film thickness unevenness when forming a large area, and can achieve high definition of a display by preventing bleeding during coating, reducing the amount of material used, and improving the yield. Therefore, it is suitable as a method for forming an organic layer in a large panel.

[0005] As a method for easily forming partitions, a method of forming them by a photolithography method using a photosensitive composition is known. Further, as a method for imparting light-shielding properties to the partitions and suppressing light leakage between pixels, a method of containing a colorant in the photosensitive composition is known.

[0006] Patent Document 1 describes a colored photosensitive resin composition used for partitions of an organic electroluminescent element, which is effective in suppressing outgas generation by using a specific organic black pigment and an alkali-soluble resin.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] In a photosensitive resin composition used for partition walls, depending on the structure of the alkali-soluble resin, thermal decomposition may occur during firing, generating fumes. Further, when a colorant is contained in the photosensitive resin composition for the purpose of ensuring light-shielding properties, the photopolymerizable component decreases and light is blocked, resulting in insufficient photocuring inside the film. Therefore, unreacted low-molecular components may be generated as fumes from inside the film during firing. As a result, the generated fume components may adhere to the anode, possibly causing display defects such as an increase in the driving voltage of the device and unevenness on the light-emitting surface.

[0009] As a result of investigations by the present inventors, it was found that the partition walls formed of the colored photosensitive composition described in Patent Document 1 are not sufficient in reducing the amount of fumes generated during firing. Note that fumes are different from outgassing. Fumes are generated during firing, while outgassing occurs from the cured product after the firing process.

[0010] The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition capable of reducing fume generation during firing.

Means for Solving the Problems

[0011] As a result of intensive investigations by the present inventor, it was found that the above problems can be solved by using a specific alkali-soluble resin, and the present invention has been completed.

[0012] That is, the gist of the present invention is as follows. [1] A photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound, wherein the (A) alkali-soluble resin contains an alkali-soluble resin (A1) which is a reaction product of the following component (a1) and the following component (a2), the following component (a3), and the following component (a4), characterized in that the photosensitive resin composition. Component (a1): At least one selected from the group consisting of an epoxy compound represented by the following formula (1) and a compound in which a substituent is bonded to the benzene ring in the epoxy compound. Component (a2): At least one selected from the group consisting of an α,β-unsaturated monocarboxylic acid and an α,β-unsaturated monocarboxylic acid ester having a carboxy group. Component (a3): At least one selected from the group consisting of a tricarboxylic acid and its anhydride. Component (a4): At least one selected from the group consisting of a tetracarboxylic acid and its anhydride. [Chemical formula] (In formula (1), X represents O, S, C(=O) or a single bond, G 1 and G 2 each independently represents an alkylene group having 1 to 4 carbon atoms, n1 and n2 each independently represent an integer of 0 to 10, and when n1 is 2 or more, a plurality of G 1 may be the same or different from each other, and when n2 is 2 or more, a plurality of G 2 may be the same or different from each other.) [2] A photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound, wherein the (A) alkali-soluble resin contains an alkali-soluble resin (A1) having two or more partial structures represented by the following formula (a-1-1), one or more partial structures represented by the following formula (a-2), and one or more partial structures represented by the following formula (a-3). A photosensitive resin composition characterized by that. [Chemical formula] (In the formula, X represents O, S, C(=O) or a single bond, G 1 and G 2 each independently represents an alkylene group having 1 to 4 carbon atoms, n1 and n2 each independently represent an integer of 0 to 10, and when n1 is 2 or more, a plurality of G 1 may be the same or different from each other, and when n2 is 2 or more, a plurality of G 2may be the same or different from each other. R 1A 、R 1B 、R 1C 、R 2A 、R 2B and R 2C each independently represents a hydrogen atom or a substituent. R 3 represents a residue derived from a tricarboxylic acid. R 4 represents a residue derived from a tetracarboxylic acid. * represents a bond. ) [3] The photosensitive resin composition according to [1], wherein the molar ratio ((a3) / (a4)) of the component (a3) to the component (a4) is 0.05 to 0.70. [4] The photosensitive resin composition according to [1] or [3], wherein the component (a3) is at least one selected from the group consisting of benzenetricarboxylic acid, its anhydride, cyclohexanetricarboxylic acid, and its anhydride. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content ratio of the alkali-soluble resin (A1) is 10% by mass or more and 95% by mass or less based on the total mass of the (A) alkali-soluble resin. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the content ratio of the (A) alkali-soluble resin is 100 parts by mass or more with respect to 100 parts by mass of the (C) ethylenically unsaturated compound. [7] The photosensitive resin composition according to any one of [1] to [6], further containing a (D) colorant. [8] The photosensitive resin composition according to [7], wherein the (D) colorant contains an organic pigment. [9] The photosensitive resin composition according to [8], wherein the organic pigment contains an organic black pigment.

[10] The photosensitive resin composition according to [9], wherein the organic black pigment contains a benzodifuranone-based organic black pigment.

[11] The photosensitive resin composition according to

[10] , wherein the benzodifuranone-based organic black pigment contains at least one organic black pigment selected from the group consisting of a compound represented by the following formula (D-1-1), its geometric isomers, its salts, and salts of its geometric isomers.

Chemical formula

[12] The photosensitive resin composition according to any one of [7] to

[11] , wherein the content ratio of the (D) colorant is 10% by mass or more based on the total solid content of the photosensitive resin composition.

[13] The photosensitive resin composition according to any one of [7] to

[12] , further comprising a phosphoric acid compound represented by the following formula (g1). [Chemical formula] (In the formula, R 51 represents a hydrogen atom or a methyl group, l represents an integer of 1 to 10, l' represents an integer of 0 to 10, and m represents a number of 1 to 3.)

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

[13] , which is for forming a partition wall.

[15] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to

[14] .

[16] A partition wall composed of the cured product according to

[15] .

[17] An organic electroluminescent element including the partition wall according to

[16] .

[18] A color filter including light-emitting nanocrystalline particles and including the partition wall according to

[16] .

[19] An image display device including the partition wall according to

[16] . [Advantages of the Invention]

[0013] According to the present invention, it is possible to provide a photosensitive resin composition capable of reducing fume generation during firing, a cured product thereof, and a partition wall, an organic electroluminescent element, a color filter, and an image display device using the cured product. [Brief Description of the Drawings]

[0014]

Figure 1

Mode for Carrying Out the Invention

[0015] Hereinafter, embodiments of the present invention will be specifically described. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. In the present invention, the following terms have the following meanings. The numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In the present invention, "(meth)acryl" means "either one or both of acrylic and methacrylic", and the same applies to "(meth)acrylate" and "(meth)acryloyl". "Acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing a (meth)acrylate having a carboxy group. "Total solid content of the photosensitive resin composition" means all components other than the solvent in the photosensitive resin composition. Even if the component other than the solvent is liquid at room temperature, the component is not included in the solvent but is included in the total solid content. "(Co)polymer" means including both a single polymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydrous)... acid" means including both an acid and its anhydride. "Monomer" is a term relative to a so-called high molecular substance (polymer), and means including not only a monomer in the narrow sense but also a dimer, a trimer, and an oligomer. "Weight average molecular weight" means the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography). "Amine value" represents, unless otherwise specified, the amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. The measurement method will be described later. "Acid value", unless otherwise specified, refers to the acid value in terms of effective solid content and is calculated by neutralization titration. Regarding pigments, "C.I." means Color Index. Percentages and parts expressed in terms of "mass" are synonymous with percentages and parts expressed in terms of "weight". "A and / or B" means "either one or both of A and B".

[0016] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound.

[0017] <(A) Alkali-soluble resin> In the present invention, the (A) alkali-soluble resin contains an alkali-soluble resin (A1). The (A) alkali-soluble resin may further contain an alkali-soluble resin other than the alkali-soluble resin (A1).

[0018] <Alkali-soluble resin (A1)> The alkali-soluble resin (A1) is a reaction product of the following component (a1) and the following component (a2) (hereinafter also referred to as "intermediate (a0)"), the following component (a3), and the following component (a4). Component (a1): At least one selected from the group consisting of an epoxy compound represented by the following formula (1) and a compound in which a substituent is bonded to the benzene ring in the epoxy compound. Component (a2): At least one selected from the group consisting of an α,β-unsaturated monocarboxylic acid and an α,β-unsaturated monocarboxylic acid ester having a carboxy group. Component (a3): At least one selected from the group consisting of a tricarboxylic acid and its anhydride. Component (a4): At least one selected from the group consisting of a tetracarboxylic acid and its anhydride.

[0019] [Chemical formula] (In the formula, X represents O, S, C(=O), or a single bond, and G 1 and G 2 each independently represent an alkylene group having 1 to 4 carbon atoms, n1 and n2 each independently represent an integer of 0 to 10, and when n1 is 2 or more, a plurality of G 1 may be the same or different from each other, and when n2 is 2 or more, a plurality of G 2 may be the same or different from each other.)

[0020] Specifically, the alkali-soluble resin (A1) is a resin obtained by further reacting component (a3) and component (a4) with the hydroxyl groups of the intermediate (a0) obtained by the reaction of component (a1) and component (a2). Since component (a4) has four carboxy groups or two carboxylic anhydride groups, by reacting component (a4), the intermediates (a0) can be crosslinked with each other, and the molecular weight of the alkali-soluble resin (A1) can be increased. In addition, by reacting component (a3), the generation of fumes during firing can be reduced. When component (a3) is reacted, compared with the case where a dicarboxylic acid (anhydride) of the same molar amount is reacted instead of component (a3), the number of carboxy groups increases, and the molecular weight and boiling point also increase. Therefore, it is less likely to thermally decompose during firing, and even when decomposed, it tends to be less likely to sublime, and it is considered that the generation of fumes during firing is significantly reduced. Also, since the number of carboxy groups in one molecule of component (a3) is more than that of dicarboxylic acid, the fact that the amount of the carboxylic acid compound for obtaining the same resin acid value can be reduced is also presumed to be a factor in suppressing fumes. Components (a1) to (a4) will be described in detail later.

[0021] In the alkali-soluble resin (A1), the molar ratio of component (a2) to 1 mol of component (a1) is preferably 1.95 mol or more, more preferably 1.99 mol or more, still more preferably 2.00 or more, and preferably 2.05 mol or less, more preferably 2.01 mol or less. The above upper and lower limits can be arbitrarily combined. When the molar number of component (a2) is at least the above lower limit value, the residual epoxy groups tend to decrease and the storage stability tends to be good. When the molar number of component (a2) is at most the above upper limit value, the unreacted remaining component (a2) tends to decrease and the fume is more suppressed.

[0022] In the alkali-soluble resin (A1), the molar ratio of component (a3) to 1 mol of component (a1) is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.10 or more, particularly preferably 0.15 or more, and preferably 0.50 mol or less, more preferably 0.30 mol or less. The above upper and lower limits can be arbitrarily combined. When the molar number of component (a3) is at least the above lower limit value, the developability tends to be good. When the molar number of component (a3) is at most the above upper limit value, the fume is more suppressed.

[0023] In the alkali-soluble resin (A1), the molar ratio of component (a4) to 1 mol of component (a1) is preferably 0.10 mol or more, more preferably 0.40 mol or more, still more preferably 0.50 mol or more, and preferably 1.00 mol or less, more preferably 0.80 mol or less. The above upper and lower limits can be arbitrarily combined. When the molar number of component (a4) is at least the above lower limit value, the film loss during development tends to be suppressed. When the molar number of component (a4) is at most the above upper limit value, the developability tends to be good.

[0024] The molar ratio of component (a3) to component (a4), ((a3) / (a4)), is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.20 or more, particularly preferably 0.40 or more, and preferably 0.90 or less, more preferably 0.70 or less, still more preferably 0.50 or less. The above upper and lower limits can be arbitrarily combined. For example, 0.05 to 0.90 is preferable, 0.05 to 0.70 is more preferable, 0.05 to 0.50 is still more preferable, 0.10 to 0.50 is even more preferable, and 0.40 to 0.50 is particularly preferable. When (a3) / (a4) is at least the above lower limit value, the solubility in the developer tends to be good. When (a3) / (a4) is at most the above upper limit value, the fume tends to be more suppressed.

[0025] The weight average molecular weight (Mw) of the alkali-soluble resin (A1) is preferably 1000 or more, more preferably 2000 or more, still more preferably 2500 or more, particularly preferably 3000 or more, and preferably 10000 or less, more preferably 8000 or less, still more preferably 6000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 10000 is preferable, 2000 to 8000 is more preferable, 2500 to 6000 is still more preferable, 3000 to 6000 is even more preferable. When the weight average molecular weight (Mw) is at least the above lower limit value, the fume is more suppressed, and there is a tendency to suppress excessive increase in solubility in the developer. When the weight average molecular weight (Mw) is at most the above upper limit value, the solubility in the developer tends to be good.

[0026] The acid value of the alkali-soluble resin (A1) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 80 mgKOH / g or more, and preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 20 mgKOH / g to 200 mgKOH / g is preferable, 50 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 120 mgKOH / g is still more preferable, and 80 mgKOH / g to 100 mgKOH / g is even more preferable. When the acid value is at least the above lower limit value, the developability is improved and the resolution tends to be good. When the acid value is at most the above upper limit value, fumes are more suppressed and the residual film rate tends to be good.

[0027] Component (a1): In formula (1), X represents O (oxygen atom), S (sulfur atom), C(=O) (carbonyl group) or a single bond. When X is a single bond, the carbon atoms to which X is bonded are directly bonded. From the viewpoints of sensitivity and fume suppression, a single bond is preferable as X.

[0028] G 1 and G 2 Examples of the alkylene group in and G include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Among these, from the viewpoints of developability and synthesis, an ethylene group is preferable.

[0029] n1 and n2 are 0 or more, preferably 8 or less, more preferably 4 or less, and still more preferably 2 or less. When n1 and n2 are at most the above upper limit value, high sensitivity and fumes can tend to be suppressed.

[0030] Examples of the substituent bonded to the benzene ring include an alkyl group and an alkoxy group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group.

[0031] From the viewpoints of sensitivity and fume suppression, the epoxy compound represented by the formula (1) having no substituent bonded to the benzene ring is preferable as the component (a1).

[0032] Component (a2): Examples of the α,β-unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, cyano-substituted products of (meth)acrylic acid, etc.

[0033] Examples of the α,β-unsaturated monocarboxylic acid ester having a carboxy group include 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid, an adduct obtained by adding lactones (e.g., ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone) to (meth)acrylic acid, an adduct obtained by adding an acid (anhydride) (e.g., (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid) to a hydroxyl group-containing (meth)acrylate (e.g., hydroxyalkyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate), (meth)acrylic acid dimer, and the like.

[0034] As component (a2), (meth)acrylic acid is preferable from the viewpoints of sensitivity and fume suppression.

[0035] Component (a3): Examples of component (a3) include benzenetricarboxylic acid, its anhydride, cyclohexanetricarboxylic acid, and its anhydride. More specifically, 1,2,4-benzenetricarboxylic acid (also referred to as trimellitic acid), 1,3,5-benzenetricarboxylic acid (also referred to as trimesic acid), 1,2,4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanedicarboxylic acid, and their anhydrides are included. Among these, 1,2,4-benzenetricarboxylic acid, its anhydride, 1,2,4-cyclohexanedicarboxylic acid, and its anhydride are preferred, and 1,2,4-cyclohexanedicarboxylic anhydride is more preferred.

[0036] Component (a4): Examples of component (a4) include pyromellitic acid, cyclohexanetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, the compounds described in JP-A-2018-004920 and JP-A-2021-064467, and their anhydrides. Among these, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides are preferred, and benzophenonetetracarboxylic anhydride is more preferred.

[0037] The intermediate (a0) which is a reaction product of component (a1) and component (a2) typically includes a compound represented by the following formula (0-1).

[0038]

Chemical formula

[0039] The α,β-unsaturated carbonyloxy group of R has a structure corresponding to component (a2). For example, when component (a2) is (meth)acrylic acid, the α,β-unsaturated carbonyloxy group of R is a (meth)acryloyloxy group.

[0040] As an example of the compound represented by formula (0-1), a compound represented by the following formula (0-1-1) can be mentioned.

[0041]

Chemical formula

[0042] R 1A 、R 1B 、R 1C 、R 2A 、R 2B and R 2C take the structure corresponding to component (a2). For example, when component (a2) is (meth) acrylic acid, R 1A and R 2A each independently represents a hydrogen atom or a methyl group, R 1B 、R 1C 、R 2B and R 2C each become a hydrogen atom.

[0043] The alkali-soluble resin (A1) which is the reaction product of the intermediate (a0), component (a3), and component (a4) typically has two or more partial structures represented by the following formula (a-1) (hereinafter also referred to as "partial structure (a-1)"), one or more partial structures represented by the following formula (a-2) (hereinafter also referred to as "partial structure (a-2)"), and one or more partial structures represented by the following formula (a-3) (hereinafter also referred to as "partial structure (a-3)"). Typically, the bond of the partial structure (a-1) is bonded to the partial structure (a-2), the partial structure (a-3), or a hydrogen atom. The bond of the partial structure (a-2) is bonded to the bond of the partial structure (a-1). The two bonds of the partial structure (a-3) are each bonded to the bonds of different partial structures (a-1) to crosslink those partial structures (a-1).

[0044]

Chemical formula

[0045] R 3 The residue derived from component (a3) of R is a group obtained by removing three carboxylic acids from the tricarboxylic acid corresponding to component (a3) (including the tricarboxylic acid corresponding to the tricarboxylic anhydride). R 4 The residue derived from component (a4) of R is a group obtained by removing four carboxylic acids from the tetracarboxylic acid corresponding to component (a4) (including the tetracarboxylic acid corresponding to the tetracarboxylic anhydride).

[0046] As an example of the partial structure (a-1), a partial structure represented by the following formula (a-1-1) can be mentioned.

[0047]

Chemical formula

[0048] The alkali-soluble resin (A1) can be produced by a known method. For example, it can be produced by the methods described in Japanese Patent Application Laid-Open No. 8-278629, Japanese Patent Application Laid-Open No. 2008-7401, Japanese Patent Application Laid-Open No. 2015-200881, and Japanese Patent Application Laid-Open No. 2016-139043.

[0049] <Alkali-soluble resin other than the alkali-soluble resin (A1)> As the alkali-soluble resin other than the alkali-soluble resin (A1), there is no particular limitation as long as it is a resin showing alkali solubility, and examples thereof include resins containing a carboxy group or a hydroxy group. More specifically, for example, epoxy (meth) acrylate resins, acrylic resins, carboxy group-containing epoxy resins, carboxy group-containing urethane resins, novolak resins, and polyvinylphenol resins can be mentioned. In particular, from the viewpoint of excellent plate-making properties, (A21) Epoxy (meth) acrylate resin, (A22) Isocyanuric skeleton resin, (A23) Acrylic copolymer resin, are preferred. These can be used alone or in combination of two or more.

[0050] <(A21) Epoxy (meth) acrylate resin> (A21) Epoxy (meth) acrylate resin is a resin obtained by reacting a hydroxyl group generated by the reaction of an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxy group in the ester moiety, with a compound having two or more substituents capable of reacting with the hydroxyl group, such as a polybasic acid and / or its anhydride. Before reacting the above polybasic acid and / or its anhydride with the hydroxyl group, a resin obtained by reacting a compound having two or more substituents capable of reacting with the hydroxyl group and then reacting the polybasic acid and / or its anhydride is also included in the (A21) epoxy (meth) acrylate resin. It should be noted that the alkali-soluble resin (A1) and the (b2) isocyanuric skeleton resin described later are not included in this classification. A resin obtained by reacting a compound having a functional group capable of further reacting with the carboxy group of the resin obtained by the above reaction is also included in the (A21) epoxy (meth) acrylate resin.

[0051] Epoxy (meth) acrylate resins, in terms of chemical structure, do not substantially have epoxy groups and are not limited to "(meth) acrylate", but are named in this way according to convention because epoxy compounds (epoxy resins) are used as raw materials and "(meth) acrylate" is a representative example.

[0052] (A21) As the epoxy (meth) acrylate resin, from the perspective of outgassing, those having an aromatic ring in the main chain can be more preferably used.

[0053] (A21) The chemical structure of the epoxy (meth) acrylate resin is not particularly limited, but from the viewpoints of developability and reliability, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (A21-I) (hereinafter, may be abbreviated as "(A21-I) epoxy (meth) acrylate resin") and / or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (A21-II) (hereinafter, may be abbreviated as "(A21-II) epoxy (meth) acrylate resin") are preferably contained.

[0054]

Chemical formula

[0055] In formula (A21-I), R A211 represents a hydrogen atom or a methyl group, R A212 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (A21-I) may be further substituted by an arbitrary substituent.

[0056]

Chemical formula

[0057] In formula (A21-II), R A213 each independently represents a hydrogen atom or a methyl group, R A215 and R A216each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer of 1 or more, and * represents a bond. The benzene ring in formula (A21-II) may be further substituted with any substituent.

[0058] <(A21-I) Epoxy (meth) acrylate resin>

[0059] [Chemical formula]

[0060] In formula (A21-I), R A211 represents a hydrogen atom or a methyl group, R A212 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (A21-I) may be further substituted with any substituent.

[0061] (R A212 ) In formula (A21-I), R A212 represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group formed by connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

[0062] The divalent aliphatic group includes linear, branched, and cyclic aliphatic groups. From the perspective of development solubility, a linear aliphatic group is preferred. On the other hand, from the perspective of reducing the penetration of the developer into the exposed area, a cyclic aliphatic group is preferred. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 1 to 10 is even more preferred. By setting the value to be equal to or greater than the lower limit value, a strong film is likely to be obtained, surface roughness during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting the value to be equal to or less than the upper limit value, it is easy to suppress the deterioration of sensitivity and film loss during development, and the resolution tends to improve.

[0063] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the perspective of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include structures in which the aforementioned divalent linear aliphatic group has, as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 12 or less, more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 12 is preferred, 1 to 10 is more preferred, and 2 to 10 is even more preferred. By setting the value to be equal to or greater than the lower limit value, a strong film is obtained and the adhesion to the substrate tends to be good. By setting the value to be equal to or less than the upper limit value, it is easy to suppress the deterioration of sensitivity and film loss during development, and the resolution tends to improve. Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, dicyclopentadiene ring, and dicyclopentane ring. From the viewpoint of the rigidity of the skeleton, groups obtained by removing two hydrogen atoms from dicyclopentadiene ring, dicyclopentane ring, and adamantane ring are preferred.

[0064] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0065] Examples of the divalent aromatic ring group include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms thereof is not particularly limited, but 4 or more is preferred, 5 or more is more preferred, and 6 or more is even more preferred. Also, 20 or less is preferred, 15 or less is more preferred, and 10 or less is even more preferred. The above upper and lower limits can be arbitrarily combined. For example, 4 to 20 is preferred, 5 to 15 is more preferred, and 6 to 10 is even more preferred. By setting it to be not less than the lower limit value, a strong film is likely to be obtained, surface roughness during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it to be not more than the upper limit value, it is easy to suppress the deterioration of sensitivity and film loss during development, and the resolution tends to improve.

[0066] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring having two free valences. The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzoisoxazole ring, a benzoisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each having two free valences. From the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

[0067] Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of development solubility, unsubstituted is preferable, and from the viewpoints of dispersibility and residual film ratio, a methyl group and an ethyl group are preferable.

[0068] Examples of the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include a group formed by linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is even more preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is even more preferable, and 2 to 3 is particularly preferable. By setting the value to be not less than the lower limit value, a strong film is likely to be obtained, surface roughness during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting the value to be not more than the upper limit value, it is easy to suppress the deterioration of sensitivity and film loss during development, and the resolution tends to be improved. The number of divalent aromatic ring groups is not particularly limited, but 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is even more preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is even more preferable, and 2 to 3 is particularly preferable. By setting the value to be equal to or greater than the lower limit value, it is easy to obtain a strong film, surface roughness during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting the value to be equal to or less than the upper limit value, it is easy to suppress the deterioration of sensitivity and film loss during development, and the resolution tends to improve.

[0069] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (A21-I-A) to (A21-I-H). From the viewpoints of the rigidity of the skeleton and the hydrophobization of the film, the group represented by the following formula (A21-I-A) is preferable. Also, from the viewpoints of dispersibility and residual film ratio, the groups represented by the following formulas (A21-I-G) and (A21-I-H) are preferable.

[0070]

Chemical formula

[0071]

Chemical formula

[0072] In formula (A21-I), k represents 1 or 2. From the viewpoints of adhesion and patterning properties, k is preferably 1. From the viewpoints of sensitivity and dispersibility, k is preferably 2. Also, both the partial structure where k is 1 and the partial structure where k is 2 may be contained in the (A21-I) epoxy (meth) acrylate resin.

[0073] The benzene ring in formula (A21-I) may be further substituted by any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and may be one or two or more. From the viewpoint of patterning characteristics, it is preferably unsubstituted.

[0074] From the viewpoint of synthetic simplicity, the partial structure represented by formula (A21-I) is preferably a partial structure represented by the following general formula (A21-I-1).

[0075]

Chemical formula

[0076] In formula (A21-I-1), R A211 , R A212 and k have the same meanings as in formula (A21-I), R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond. The benzene ring in formula (A21-I-1) may be further substituted by any substituent.

[0077] The polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning characteristics, preferably, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferably, tetrahydrophthalic acid and biphenyltetracarboxylic acid.

[0078] The benzene ring in formula (A21-I-1) may be further optionally substituted with any substituent. As the substituent, those exemplified for the benzene ring in formula (A21-I) can preferably be adopted.

[0079] (A21-I) The number of the partial structures represented by formula (A21-I-1) contained in one molecule of the epoxy (meth) acrylate resin may be one or two or more. For example, those where R X is a hydrogen atom and those where R X is a polybasic acid residue may be mixed.

[0080] (A21-I) The number of the partial structures represented by formula (A21-I) contained in one molecule of the epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3 or more is more preferable. Also, 20 or less is preferable, and 15 or less is more preferable. The above upper and lower limits can be arbitrarily combined. 1 to 20 is preferable, 1 to 15 is more preferable, and 3 to 15 is even more preferable. By setting it to be equal to or higher than the lower limit value, a strong film is likely to be obtained, and the surface roughness that occurs during development tends not to occur. By setting it to be equal to or lower than the upper limit value, it is easy to suppress the deterioration of sensitivity and the film reduction during development, and the resolution tends to improve.

[0081] Specific examples of the (A21-I) epoxy (meth) acrylate resin are given below. In the examples, * indicates a bond.

[0082] [Chemical formula]

[0083] [Chemical formula]

[0084] [Chemical formula]

[0085] [Chemical formula]

[0086]

Chem.

[0087]

Chem.

[0088] <(A21-II) epoxy (meth)acrylate resin>

[0089]

Chem.

[0090] In formula (A21-II), R A213 each independently represents a hydrogen atom or a methyl group, R A215 and R A216 each independently represent a divalent aliphatic group which may have a substituent, m and n each independently represent an integer from 0 to 2, R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer of 1 or more, and * represents a bond. The benzene ring in formula (A21-II) may be further substituted with any substituent

[0091] (R A215 , R A216 ) In formula (A21-II), R A215 and R A216 each independently represent a divalent aliphatic group which may have a substituent.

[0092] The divalent aliphatic group includes linear, branched, and cyclic aliphatic groups. From the perspective of development solubility, a linear aliphatic group is preferred, while from the perspective of reducing the penetration of the developer into the exposed area, a cyclic aliphatic group is preferred. The number of carbon atoms is not particularly limited, but 1 or more is preferred, 3 or more is more preferred, and 6 or more is even more preferred. Also, 20 or less is preferred, 15 or less is more preferred, and 10 or less is even more preferred. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferred, 3 to 15 is more preferred, and 6 to 10 is even more preferred. By setting it to be equal to or greater than the lower limit value, a strong film is easily obtained, surface roughness during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it to be equal to or less than the upper limit value, it is easy to suppress the deterioration of sensitivity and film loss during development, and the resolution tends to improve.

[0093] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the perspective of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include structures having, as side chains, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group in the aforementioned divalent linear aliphatic group. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but 1 or more is preferred, and 2 or more is more preferred. Also, 12 or less is preferred, and 10 or less is more preferred. The above upper and lower limits can be arbitrarily combined. For example, 1 to 12 is preferred, and 2 to 10 is more preferred. By setting it to be equal to or greater than the lower limit value, a strong film is obtained, and the adhesion to the substrate tends to be good. By setting it to be equal to or less than the upper limit value, it is easy to suppress the deterioration of sensitivity and film loss during development, and the resolution tends to improve. Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a dicyclopentadiene ring. From the viewpoint of the rigidity of the skeleton, groups obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring are preferred.

[0094] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0095] (m, n) In formula (A21-II), m and n each independently represent an integer of 0 to 2. By setting the value to be not less than the lower limit value, the patterning appropriateness becomes good, and the surface roughness generated during development tends not to occur. Also, by setting the value to be not more than the upper limit value, the developability tends to be good. From the viewpoint of developability, it is preferable that m and n are 0. From the viewpoints of patterning appropriateness and suppressing the surface roughness generated during development, it is preferable that m and n are 1 or more.

[0096] (R α ) In formula (A21-II-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent. Examples of the cyclic hydrocarbon group include an aliphatic ring group or an aromatic ring group.

[0097] The number of rings of the aliphatic ring group is not particularly limited, but 1 or more is preferable, and 2 or more is more preferable. Also, 6 or less is preferable, 4 or less is more preferable, and 3 or less is even more preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 6 is preferable, 1 to 4 is more preferable, 1 to 3 is even more preferable, and 2 to 3 is particularly preferable. By setting the value to be not less than the lower limit value, a strong film is likely to be obtained, and the surface roughness generated during development tends not to occur. By setting the value to be not more than the upper limit value, the patterning characteristics tend to be good. The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Also, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, 4 to 40 is preferable, 4 to 30 is more preferable, 6 to 20 is even more preferable, and 8 to 15 is particularly preferable. By setting it to be equal to or higher than the lower limit value, a strong film is likely to be obtained, and surface roughness during development is less likely to occur. By setting it to be equal to or lower than the upper limit value, the patterning characteristics tend to be good. Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of strong film properties, an adamantane ring is preferable.

[0098] The number of rings in the aromatic cyclic group is not particularly limited, but is preferably 1 or more, preferably 2 or more, and more preferably 3 or more. Also, it is preferably 10 or less, and more preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is even more preferable, and 3 to 5 is particularly preferable. By setting it to be equal to or higher than the lower limit value, a strong film is likely to be obtained, and surface roughness during development is less likely to occur. By setting it to be equal to or lower than the upper limit value, the patterning characteristics tend to be good. Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Also, the number of carbon atoms in the aromatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Also, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, 4 to 30 is preferable, 5 to 20 is more preferable, 6 to 15 is even more preferable. By setting it to be equal to or higher than the lower limit value, a strong film is likely to be obtained, and surface roughness during development is less likely to occur. By setting it to be equal to or lower than the upper limit value, the patterning characteristics tend to be good. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of development solubility, a fluorene ring is preferred.

[0099] Examples of the substituent that the cyclic hydrocarbon group may have include, for example, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, unsubstituted is preferred.

[0100] From the viewpoint of strong film hardness, α R is preferably a monovalent aliphatic ring group, more preferably an adamantyl group.

[0101] p represents an integer of 1 or more, preferably 2 or more. Also, 3 or less is preferred. For example, 1 to 3 is preferred, and 2 to 3 is more preferred. By setting it to be not less than the lower limit value, the film hardness and the remaining film ratio tend to be good. By setting it to be not more than the upper limit value, the developability tends to be good.

[0102] The benzene ring in the formula (A21-II-1) may be further substituted with an arbitrary substituent. Examples of the substituent include, for example, a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and it may be one or two or more. From the viewpoint of patterning characteristics, it is preferably unsubstituted.

[0103] Specific examples of the partial structure represented by the formula (A21-II-1) are given below.

[0104]

Chemical formula

[0105] [Chemistry]

[0106] [Chemistry]

[0107] [Chemistry]

[0108] [Chemistry]

[0109] [Chemistry]

[0110] In formula (A21-II-2), R A213 , R A215 , R A216 , m, n, R α and p are synonymous with formula (A21-II), and R Z represents a hydrogen atom or a polybasic acid residue.

[0111] The polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Additionally, another OH group may be removed and shared with R Z in another molecule represented by formula (A21-II-2). That is, a plurality of formula (A21-II-2) may be linked via R Z . Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid. From the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.

[0112] (A21-II) The number of the partial structures represented by the formula (A21-II-2) contained in one molecule of the epoxy (meth) acrylate resin may be one kind or two or more kinds. For example, R Z in which is a hydrogen atom and R Z in which is a polybasic acid residue may be mixed.

[0113] (A21-II) The number of the partial structures represented by the formula (A21-II) contained in one molecule of the epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3 or more is more preferable. Also, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferable, 1 to 15 is more preferable, and 3 to 10 is further preferable. By setting the value to be not less than the lower limit value, a strong film is likely to be obtained, and surface roughness generated during development is likely not to occur. By setting the value to be not more than the upper limit value, deterioration of sensitivity and film reduction are likely to be suppressed, and the resolution tends to be improved.

[0114] (A21) The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, even more preferably 3000 or more, still more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 10000 or less, more preferably 8000 or less, further preferably 7000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 10000 is preferable, 1500 to 10000 is more preferable, 1500 to 8000 is further preferable, 2000 to 8000 is even more preferable, and 2000 to 7000 is particularly preferable. By setting it to be not less than the lower limit value, the residual film rate of the photosensitive resin composition tends to be good. By setting it to be not more than the upper limit value, the solubility in the developer tends to be good.

[0115] (A21) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 20 mgKOH / g to 200 mgKOH / g is preferable, 60 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 130 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is even more preferable. By setting it to be not less than the lower limit value, the development solubility is improved and the resolution tends to be good. By setting it to be not more than the upper limit value, the residual film rate of the photosensitive resin composition tends to be good.

[0116] <(A22) Isocyanuric skeleton-containing resin> (A22) The isocyanuric skeleton-containing resin is an isocyanuric skeleton-containing resin having an ethylenic double bond and a carboxy group. (A22) The isocyanurate skeleton-containing resin has an isocyanurate skeleton, an ethylenic double bond, and a carboxy group, thereby improving chemical resistance and heat resistance, and reducing the amount of decomposition products during development and firing, so that the driving voltage tends to be low in an organic electric field element. (A22) The isocyanurate skeleton-containing resin is not particularly limited as long as it has an ethylenic double bond, a carboxy group, and an isocyanurate skeleton. Examples thereof include the isocyanurate skeleton-containing resin (A22-1) and the isocyanurate skeleton-containing resin (A22-2) shown below.

[0117] <<Isocyanurate Skeleton-Containing Resin (A22-1)>> The isocyanurate skeleton-containing resin (A22-1) is a resin obtained by reacting a reaction product of an epoxy group-containing compound having an isocyanurate skeleton with an α,β-unsaturated monocarboxylic acid and / or an ester compound, further with a polybasic acid and / or its anhydride, etc.

[0118] Examples of the epoxy group-containing compound having an isocyanurate skeleton include compounds represented by the following general formula (A22-1-1).

[0119]

Chemical formula

[0120] In formula (A22-1-1), R A224 ~R A226 each independently represents an alkylene group, and the alkylene group may be interrupted by an etheric oxygen atom in the middle.

[0121] The alkylene group preferably has 1 or more carbon atoms. Also, preferably 6 or less carbon atoms, more preferably 4 or less, and even more preferably 2 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 6 is preferable, 1 to 4 is more preferable, and 1 to 2 is even more preferable. The alkylene group may be linear or branched. By setting it below the above upper limit value, developability becomes good, and the gas barrier property tends to be improved. Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, and an n-hexylene group. Examples of the alkylene group interrupted by an etheric oxygen atom in the middle include a group in which 1 to 10 carbon atoms of a linear or branched alkylene chain having 4 to 30 carbon atoms are replaced by oxygen atoms, and examples thereof include a group in which 2 to 9 ethoxy groups are linked and a group including a group in which 2 to 7 propoxy groups are linked. Among these, from the viewpoint of gas barrier properties, a methylene group, an ethylene group, and an n-propylene group are preferable, and a methylene group is more preferable.

[0122] Examples of the α,β-unsaturated monocarboxylic acid and / or ester compound include the same ones as those of the component (a2). From the viewpoint of sensitivity, (meth)acrylic acid is preferable.

[0123] As a method for adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy group-containing compound having an epoxy resin isocyanuric skeleton, the same method as that for an epoxy (meth)acrylate resin can be used.

[0124] Examples of the polybasic acid and / or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

[0125] Preferably, they are succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Particularly preferably, they are pyromellitic acid and its anhydride.

[0126] The addition reaction of a polybasic acid and / or its anhydride can be carried out using the same method as that for the epoxy (meth)acrylate resin (A21).

[0127] <<Isocyanuric skeleton-containing resin (A22-2)>> The isocyanuric skeleton-containing resin (A22-2) is a resin obtained by reacting a polyisocyanate compound having an isocyanuric skeleton with an acid or acid anhydride and then reacting the resulting compound with an epoxy group-containing (meth)acrylate compound. Examples of the resin of (A22-2) include the resins and their intermediates described in JP-A-2020-75994, JP-A-2023-55304, JP-A-2023-55622, and JP-A-2023-55623.

[0128] The weight average molecular weight (Mw) of the isocyanuric skeleton-containing resin (A22) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, still more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 10000 or less, more preferably 8000 or less, and further preferably 7000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 10000 is preferable, 1500 to 10000 is more preferable, 1500 to 8000 is further preferable, 2000 to 8000 is still more preferable, 2000 to 7000 is even more preferable, 3000 to 7000 is particularly preferable, 4000 to 7000 is more particularly preferable, and 5000 to 7000 is most preferable. By setting the value to be not less than the lower limit value, there is a tendency to suppress the excessive increase in solubility in the developer. By setting the value to be not more than the upper limit value, there is a tendency for the solubility in the developer to be easily made good.

[0129] (A22) The acid value of the resin containing an isocyanurate skeleton is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, still more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 20 to 200 mgKOH / g is preferable, 40 to 200 mgKOH / g is more preferable, 60 to 150 mgKOH / g is still more preferable, 80 to 150 mgKOH / g is even more preferable, and 100 to 150 mgKOH / g is particularly preferable. By setting it to be not less than the lower limit value, the development solubility is improved, and the resolution tends to be good. By setting it to be not more than the upper limit value, the residual film ratio of the photosensitive resin composition tends to be good.

[0130] <(A23) Acrylic copolymer resin> (A) As the alkali-soluble resin, from the viewpoint of compatibility with pigments, dispersants, etc., it is preferable to use (A23) acrylic copolymer resin, and those described in Japanese Patent Application Laid-Open No. 2014-137466 can be preferably used.

[0131] (A23) Examples of the acrylic copolymer resin include copolymers of an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as "unsaturated monomer (A23-1)") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as "unsaturated monomer (A23-2)"). Examples of the unsaturated monomer (A23-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids with a valency of 2 or more such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl]; mono(meth)acrylates of polymers having a carboxy group and a hydroxy group at both ends such as ω-carboxypolycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid. These unsaturated monomers (A23-1) can be used alone or in combination of two or more.

[0132] Examples of the unsaturated monomer (A23-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

[0133] methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 2,6(Meth)acrylic acid esters such as decan-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of paracumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

[0134] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane; Macromonomers having a mono(meth)acryloyl group at the terminal of a polymer molecular chain such as polystyrene, poly(methyl (meth)acrylate), poly(n-butyl (meth)acrylate), polysiloxane; can be mentioned. These unsaturated monomers (A23-2) can be used alone or in combination of two or more.

[0135] In the copolymer of the unsaturated monomer (A23-1) and the unsaturated monomer (A23-2), when the total of the unsaturated monomer (A23-1) and the unsaturated monomer (A23-2) is 100% by mass, the copolymerization ratio of the unsaturated monomer (A23-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b3-1) within such a range, there is a tendency to obtain a photosensitive resin composition excellent in alkali developability and storage stability.

[0136] Examples of the copolymer of the unsaturated monomer (A23-1) and the unsaturated monomer (A23-2) include the copolymers disclosed in JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, and JP-A-2004-101728. The copolymer of the unsaturated monomer (A23-1) and the unsaturated monomer (A23-2) can be produced by a known method. For example, the structure, Mw, and Mw / Mn (Mn is the number average molecular weight) can also be controlled by the methods disclosed in JP-A-2003-222717, JP-A-2006-259680, and WO 2007 / 029871.

[0137] As the (A23) acrylic copolymer resin, the resins described in WO 2016 / 194619 and WO 2017 / 154439 may also be used.

[0138] <(B) Photoinitiator> The photosensitive resin composition of the present invention contains a (B) photoinitiator. (B) The photoinitiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. Additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added and used as necessary. Examples of the photoinitiator include oxime ester compounds, metallocene compounds including titanocene compounds, hexaarylbiimidazole derivatives, halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and α-aminoalkylphenone derivatives.

[0139] As a photoinitiator, an oxime ester compound is particularly effective in terms of sensitivity and plate-making properties. For example, in the case of using a compound containing an ethylenically unsaturated bond or a colorant, an oxime ester compound having such excellent sensitivity is particularly useful. The oxime ester compound has a high quantum yield of the photoreaction and high activity of the generated radicals, so it has high sensitivity and is stable against thermal reactions, and it is possible to obtain a highly sensitive photosensitive resin composition in a small amount.

[0140] Examples of the oxime ester compound include compounds represented by the following formula (C1).

[0141]

Chemical formula

[0142] In formula (C1), R c21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R c21b represents an arbitrary substituent containing an aromatic ring. R c22a represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent. n represents an integer of 0 or 1.

[0143] R c21a The number of carbon atoms of the alkyl group in is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, 1 or more is preferable, 2 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is even more preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferable, 2 to 15 is more preferable, and 2 to 10 is even more preferable. For example, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0144] R c21a Examples of the aromatic ring group in include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 30 is preferable, 5 to 20 is more preferable, and 5 to 12 is still more preferable.

[0145] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group formed by linking these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group formed by linking these are preferable, and a linked alkoxy group is more preferable. From the viewpoint of developability, R c21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having a linked alkoxy group as a substituent.

[0146] R c21bExamples include an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group, or an optionally substituted indolyl group. From the viewpoint of sensitivity, an optionally substituted carbazolyl group is preferred. From the viewpoint of electrical reliability, an optionally substituted diphenyl sulfide group is preferred.

[0147] R c22a The number of carbon atoms of the alkanoyl group in R is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, 2 or more is preferable, 20 or less is preferable, 15 or less is more preferable, 10 or less is further preferable, and 5 or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 2 to 20 is preferable, 2 to 15 is more preferable, 2 to 10 is further preferable, and 2 to 5 is even more preferable. Examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group. Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0148] R c22a The number of carbon atoms of the aroyl group in R is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, 7 or more is preferable, 8 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further preferable. Examples of the aroyl group include a benzoyl group and a naphthoyl group. Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted. From the viewpoint of sensitivity, R c22a is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

[0149] (B) As the photopolymerization initiator, for example, the photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, International Publication No. 2012 / 68879, International Publication No. 2021 / 175855, and Japanese Patent Application Laid-Open No. 2016-133574 can be used.

[0150] Examples of the metallocene compound include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophen-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophen-1-yl), dicyclopentadienyltitanium di(2,6-difluorophen-1-yl), dicyclopentadienyltitanium di(2,4-difluorophen-1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophen-1-yl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophen-1-yl), and dicyclopentadienyltitanium [2,6-di-fluoro-3-(pyrro-1-yl)-phen-1-yl).

[0151] Examples of hexaarylbiimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0152] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0153] Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0154] Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

[0155] (B) The photoinitiator may be used alone or in combination of two or more kinds. (B) If necessary, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photoinitiator for the purpose of enhancing the sensitivity. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, dyes having a dialkylaminobenzene skeleton described in JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818.

[0156] As the sensitizing dye, an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine and other p-dialkylaminophenyl group-containing compounds are preferable, and 4,4'-dialkylaminobenzophenone is particularly preferable. The sensitizing dye may be used alone or in combination of two or more.

[0157] As the polymerization accelerator, for example, aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, 4-dimethylaminopropiophenone; aliphatic amines such as n-butylamine, N-methyldiethanolamine, 2-dimethylaminoethyl benzoate; and mercapto compounds described below are used. The polymerization accelerator may be used alone or in combination of two or more.

[0158] <(C) Ethylenically unsaturated compound> The photosensitive resin composition of the present invention contains a (C) ethylenically unsaturated compound. By containing the (C) ethylenically unsaturated compound, the sensitivity is improved. (C) The ethylenically unsaturated compound is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples of the (C) ethylenically unsaturated compound include (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and monoester of polyhydric or monohydric alcohol.

[0159] As the (C) ethylenically unsaturated compound, a polyfunctional ethylenically unsaturated monomer having two or more ethylenically unsaturated groups in one molecule is preferable. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenically unsaturated monomer is not particularly limited, but two or more are preferable, four or more are more preferable, five or more are further preferable, and eight or less are preferable, and seven or less are more preferable. The above upper and lower limits can be arbitrarily combined. For example, 2 to 8 are preferable, 2 to 7 are more preferable, 4 to 7 are further preferable, and 5 to 7 are particularly preferable. By setting the value to be not less than the lower limit value, there is a tendency to achieve high sensitivity. Also, by setting the value to be not more than the upper limit value, the solubility in the solvent tends to be improved. Examples of the polyfunctional ethylenically unsaturated monomer include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; esters obtained by an esterification reaction of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

[0160] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.; methacrylic esters obtained by replacing these acrylates with methacrylates; itaconic acid esters obtained by replacing these acrylates with itaconates; crotonic acid esters obtained by replacing these acrylates with crotonates; maleic acid esters obtained by replacing these acrylates with maleates.

[0161] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, etc.

[0162] The esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyhydric hydroxy compounds are not necessarily single substances. Examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0163] In addition, examples of the polyfunctional ethylenically unsaturated monomer used in the present invention include urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

[0164] Examples of urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Mitsubishi Chemical Corporation).

[0165] From the viewpoint of curability, as the (C) ethylenically unsaturated compound, it is preferable to use urethane (meth) acrylates obtained by reacting an alkyl (meth) acrylate, a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate, and it is more preferable to use a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate. (C) The ethylenically unsaturated compound may be used alone or in combination of two or more.

[0166] <(D) Colorant> The photosensitive resin composition of the present invention preferably contains a (D) colorant. By containing the (D) colorant, appropriate light absorbency can be obtained, and particularly appropriate light shielding properties can be obtained when used for forming light shielding members such as partition walls.

[0167] (D) The colorant is not particularly limited, and a pigment or a dye may be used. From the viewpoint of durability, it is preferable to use a pigment.

[0168] (D) The pigment contained in the colorant may be used alone or in combination of two or more. From the viewpoints of uniformly shielding light in the visible region and achieving both the optical density per 1 μm thickness of the coating film obtained by curing the photosensitive resin composition (hereinafter also referred to as "OD per unit thickness" or "unit OD"), it is preferable to use two or more.

[0169] (D) The pigment that can be used as the colorant is not particularly limited, but from the viewpoints of high dielectric and low dielectric constant, an organic pigment is preferable. Examples of the organic pigment include organic coloring pigments and organic black pigments. Here, the organic coloring pigment means an organic pigment that exhibits a color other than black, and examples thereof include red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

[0170] From the viewpoints of suppressing ultraviolet absorption, having high curability, and easily controlling the shape of the cured product, it is preferable to use an organic coloring pigment. From the viewpoint of light shielding property, it is preferable to use an organic black pigment.

[0171] The organic coloring pigment may be used alone or in combination of two or more. In particular, it is more preferable to use a combination of organic coloring pigments having different colors, and it is even more preferable to use a combination of organic coloring pigments that exhibit a color close to black by combination.

[0172] The chemical structures of these organic coloring pigments are not particularly limited, and examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. Specific examples of the pigments that can be used are shown by pigment numbers below. In "C.I. Pigment Red 2" and the like listed below, "C.I." means Color Index.

[0173] Examples of red pigments include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. From the viewpoints of light-shielding property and dispersibility, preferably C.I. Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment Red 177, 209, 224, 254. In terms of dispersibility and light-shielding property, it is preferable to use C.I. Pigment Red 177, 254, 272. When the photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. From this viewpoint, it is more preferable to use C.I. Pigment Red 254, 272.

[0174] Examples of orange pigments include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. From the viewpoints of dispersibility and light-shielding property, it is preferable to use C.I. Pigment Orange 13, 43, 64, 72. When the photosensitive resin composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. From this viewpoint, it is more preferable to use C.I. Pigment Orange 64, 72.

[0175] Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. From the viewpoint of light-shielding property, preferably C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, and more preferably C.I. Pigment Blue 15:6 can be mentioned. From the viewpoints of dispersibility and light-shielding property, it is preferable to use C.I. Pigment Blue 15:6, 16, 60. When the photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. From this viewpoint, it is more preferable to use C.I. Pigment Blue 60.

[0176] Examples of the purple pigment include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. From the viewpoint of light-shielding property, preferably C.I. Pigment Violet 19, 23, 29, and more preferably C.I. Pigment Violet 23 can be mentioned. From the viewpoints of dispersibility and light-shielding property, it is preferable to use C.I. Pigment Violet 23, 29. When the photosensitive resin composition is cured with ultraviolet rays, as the purple pigment, it is preferable to use one having a low ultraviolet absorption rate, and from such a viewpoint, it is more preferable to use C.I. Pigment Violet 29.

[0177] Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. Preferably, C.I. Pigment Green 7, 36 can be mentioned.

[0178] Examples of yellow pigments include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Preferably, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185; more preferably, C.I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

[0179] From the viewpoints of the light shielding property of the cured product and the control of the shape, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments.

[0180] From the viewpoints of the light shielding property of the cured product and the control of the shape, it is preferable that it contains at least one or more of the following pigments. Red pigment: C.I. Pigment Red 177, 254, 272 Orange pigment: C.I. Pigment Orange 43, 64, 72 Blue pigment: C.I. Pigment Blue 15:6, 60 Violet pigment: C.I. Pigment Violet 23, 29

[0181] When two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited. However, from the viewpoint of light shielding properties, it preferably contains at least one selected from the group consisting of red pigments and orange pigments, and at least one selected from the group consisting of blue pigments and violet pigments. The combination of colors is not particularly limited. However, from the viewpoint of light shielding properties, examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a violet pigment.

[0182] Examples of the organic black pigment include perylene-based organic black pigments, aniline-based organic black pigments, benzodifuranone-based organic black pigments, etc. Examples of the perylene-based organic black pigments include Lumogen Black (registered trademark) FK4281, K0087, Paliogen Black (registered trademark) EH0788 (all manufactured by BASF), etc. Examples of the aniline-based organic black pigments include Paliotol Black (registered trademark) L0080, D0080, K0080 (all manufactured by BASF). Among these, from the viewpoints of dispersibility and developability, benzodifuranone-based organic black pigments are preferred.

[0183] The benzodifuranone-based organic black pigment preferably contains at least one organic black pigment (hereinafter sometimes referred to as "organic black pigment (D-1)") selected from the group consisting of a compound represented by the following formula (D-1-1) (hereinafter sometimes referred to as "compound (D-1-1)"), its geometric isomers, its salts, and salts of its geometric isomers, from the viewpoints of light shielding properties and suppressing ultraviolet absorption to easily control the taper shape.

[0184]

Chemical formula

[0185] In formula (D-1-1), R 611 and R 616 each independently represent a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom; R 612 、R 613 、R 614 、R 615 、R 617 、R 618 、R 619 and R 620 each independently represents a hydrogen atom, a halogen atom, R 621 、COOH, COOR 621 、COO - 、CONH2, CONHR 611 、CONR 621 R 622 、CN, OH, OR 621 、COCR 621 、OOCNH2, OOCNHR 621 、OOCNR 621 R 622 、NO2, NH2, NHR 621 、NR 621 R 622 、NHCOR 622 、NR 621 COR 622 、N=CH2, N=CHR 621 、N=CR 621 R 622 、SH, SR 621 、SOR 621 、SO2R 621 、SO3R 621 、SO3H, SO3 - 、SO2NH2, SO2NHR 621 or SO2NR 621 R 622 represents; R 612 and R 613 、R 613 and R 614 、R 614 and R 615 、R 617 and R 618 、R 618 and R 619 、and R 619 and R 620 at least one combination selected from the group consisting of may be directly bonded to each other or may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR 621 bridge; R 621 and R 622Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

[0186] Compound (D-1-1) and the geometric isomers of compound (D-1-1) have the following core structure (however, the substituents in the structural formula are omitted). Among these, the trans-trans isomer is probably the most stable.

[0187]

Chemical formula

[0188] When compound (D-1-1) is anionic, it is preferably a salt in which the charge is compensated by any known suitable cation, such as a metal, organic, inorganic, or organometallic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Also, when the geometric isomer of compound (D-1-1) is anionic, it is preferably a similar salt.

[0189] In the substituents of formula (D-1-1) and their definitions, the following are preferred because the shielding rate tends to be high. This is because the following substituents are considered to have no absorption and do not affect the hue of the pigment. R 612 、R 614 、R 615 、R 617 、R 619 and R 620 Each independently is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom. R 613 and R 618Each is independently, preferably a hydrogen atom, NO2, OCH3, OC2H5, bromine atom, chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H or SO3 - and more preferably a hydrogen atom or SO3H, and particularly preferably a hydrogen atom.

[0190] R 611 and R 616 Each is independently, preferably a hydrogen atom, CH3 or CF3, and more preferably a hydrogen atom. Preferably, R 611 and R 616 R 612 and R 617 R 613 and R 618 R 614 and R 619 and R 615 and R 620 at least one combination selected from the group consisting of is the same, and more preferably, R 611 is the same as R 616 R 612 is the same as R 617 R 613 is the same as R 618 R 614 is the same as R 619 and R 615 R 620 is the same as.

[0191] The alkyl group having 1 to 12 carbon atoms is, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.

[0192] The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexyl group, a tsujyl group, a norbornyl group, a bornyl group, a norcaril group, a caril group, a methyl group, a norpinyl group, a pinyl group, an adamantan-1-yl group or an adamantan-2-yl group.

[0193] The alkenyl group having 2 to 12 carbon atoms is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 1,3-butadien-2-yl group, a 2-penten-1-yl group, a 3-penten-2-yl group, a 2-methyl-1-buten-3-yl group, a 2-methyl-3-buten-2-yl group, a 3-methyl-2-buten-1-yl group, a 1,4-pentadien-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a dodecenyl group.

[0194] The cycloalkenyl group having 3 to 12 carbon atoms is, for example, a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, a 2,4-cyclohexadien-1-yl group, a 1-p-menthen-8-yl group, a 4(10)-tsujen-10-yl group, a 2-norbornen-1-yl group, a 2,5-norbornadien-1-yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camfenyl group.

[0195] The alkynyl group having 2 to 12 carbon atoms is, for example, a 1-propyn-3-yl group, a 1-butyn-4-yl group, a 1-pentyn-5-yl group, a 2-methyl-3-butyn-2-yl group, a 1,4-pentadiyn-3-yl group, a 1,3-pentadiyn-5-yl group, a 1-hexyn-6-yl group, a cis-3-methyl-2-penten-4-yn-1-yl group, a trans-3-methyl-2-penten-4-yn-1-yl group, a 1,3-hexadiyn-5-yl group, a 1-octyn-8-yl group, a 1-nonin-9-yl group, a 1-decin-10-yl group or a 1-dodecin-12-yl group.

[0196] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0197] The organic black pigment (D-1) preferably contains at least one selected from the group consisting of a compound represented by the following formula (D2) (hereinafter also referred to as "compound (D2)"), its geometric isomers, its salts, and salts of its geometric isomers.

[0198] [Chemical formula]

[0199] Examples of the organic black pigment containing at least one selected from the group consisting of compound (D2), its geometric isomers, its salts, and salts of its geometric isomers include, for example, Irgaphor® Black S 0100 CF (manufactured by BASF) under the trade name.

[0200] The organic black pigment (D-1) is preferably dispersed and used by a dispersant, a solvent, and a method described later. In addition, when a sulfonic acid derivative of compound (D-1-1), particularly a sulfonic acid derivative of compound (D2), is present during dispersion, the dispersibility and storage stability may be improved. Therefore, it is preferable that the organic black pigment contains such a sulfonic acid derivative.

[0201] On the other hand, from the viewpoint of higher light-shielding properties, it is preferable to use an inorganic black pigment. Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Carbon black can be preferably used from the viewpoints of light-shielding properties and image characteristics.

[0202] Examples of carbon black include the following carbon blacks. Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B. Manufactured by Degussa: Printex (registered trademark, the same hereinafter). 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170. Manufactured by Cabot Corporation: Monarch (registered trademark, the same hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, the same hereinafter) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 550R, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, the same hereinafter) XC72R, ELFTEX (registered trademark)-8. Manufactured by Birla Corporation: RAVEN (registered trademark, the same hereinafter) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000.

[0203] As the carbon black, those with an acid-treated surface may be used. For example, the carbon black described in Japanese Patent Publication No. 3674086 can be preferably used. Also, carbon black coated with a resin may be used. Using carbon black coated with a resin has the effect of improving the adhesion to the glass substrate and the volume resistivity. As the carbon black coated with a resin, for example, the carbon black described in Japanese Unexamined Patent Application Publication No. 09-71733 can be preferably used. In terms of volume resistance and dielectric constant, resin-coated carbon black is preferably used.

[0204] These pigments are preferably used after being dispersed so that the average particle diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.25 μm or less. Here, the standard for the average particle diameter is the number of pigment particles. In the photosensitive resin composition of the present invention, the average particle diameter of the pigment is a value determined from the pigment particle diameter measured by dynamic light scattering (DLS). The particle diameter measurement is performed on a sufficiently diluted photosensitive resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, follow that concentration.), and the measurement is carried out at 25°C.

[0205] In addition to the above-mentioned organic coloring pigments and black pigments, dyes may also be used. Examples of dyes that can be used as the colorant (D) include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0206] Examples of azo dyes include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, and C.I. Mordant Black 7.

[0207] Examples of anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60.

[0208] Examples of phthalocyanine dyes include C.I. Vat Blue 5. Examples of quinoneimine dyes include C.I. Basic Blue 3 and C.I. Basic Blue 9. Examples of quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, and C.I. Disperse Yellow 64. Examples of nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42.

[0209] <(E) Dispersant> When the photosensitive coloring composition contains (D) a colorant, for the purpose of ensuring quality stability, it is preferable that the photosensitive coloring composition contains (E) a dispersant in order to finely disperse the (D) colorant and stabilize the dispersion state of the (D) colorant. As the (E) dispersant, a polymer dispersant having a functional group is preferable. From the viewpoint of dispersion stability, for example, a polymer dispersant having any one or more of a carboxy group; a phosphoric acid group; a sulfonic acid group; or a salt thereof; a primary, secondary, or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is more preferable, and a polymer dispersant having any one or more of a tertiary amino group; a quaternary ammonium base is even more preferable because it can disperse the pigment with a small amount of dispersant and is likely to lower the driving voltage when an organic light-emitting device is fabricated.

[0210] Examples of polymeric dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of a monomer and a macromonomer having an amino group, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants.

[0211] Examples of such dispersants include trade names such as EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemical Industries, Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Inc.). The polymer dispersing agent may be used alone or in combination of two or more kinds.

[0212] From the viewpoint of pigment dispersibility, the (E) dispersant preferably contains either one or both of a urethane-based polymer dispersant having a functional group and an acrylic-based polymer dispersant, and it is particularly preferable that the (E) dispersant contains an acrylic-based polymer dispersant. From the standpoint of dispersibility and storage stability, polymer dispersants having a basic functional group and either or both of a polyester bond and a polyether bond are preferred.

[0213] Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic-based) (all manufactured by BYK-Chemie).

[0214] The amine value of the polymer dispersant having a basic functional group is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, even more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. Also, it is preferably 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, still more preferably 100 mgKOH / g or less, even more preferably 90 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 140 mgKOH / g is preferable, 10 to 120 mgKOH / g is more preferable, 20 to 100 mgKOH / g is still more preferable, 40 to 90 mgKOH / g is even more preferable, and 50 to 80 mgKOH / g is particularly preferable. By setting it to be not less than the lower limit value, the dispersibility tends to be good. By setting it to be not more than the upper limit value, the compatibility with the (A) alkali-soluble resin tends to be good.

[0215] From the viewpoint of dispersibility, the acrylic dispersant is preferably a block copolymer composed of an A block having the above functional group and a B block not having the above functional group. Examples of such a block copolymer include an A-B block copolymer and a B-A-B block copolymer. In the A block, in addition to the partial structure derived from the unsaturated group-containing monomer containing the above functional group, a partial structure derived from an unsaturated group-containing monomer not containing the above functional group may be included, and these may be contained in the A block in any mode of random copolymerization or block copolymerization. From the viewpoint of dispersibility, the B block is preferably composed only of a partial structure derived from an unsaturated group-containing monomer not containing the above functional group, and a partial structure derived from two or more kinds of monomers may be contained in one B block, and these may be contained in the B block in any mode of random copolymerization or block copolymerization.

[0216] Such an acrylic dispersant may contain an amino group. The amine value of the acrylic dispersant is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, yet more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. Also, it is preferably 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, still more preferably 100 mgKOH / g or less, yet more preferably 90 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 140 mgKOH / g is preferable, 10 to 120 mgKOH / g is more preferable, 20 to 100 mgKOH / g is still more preferable, 40 to 90 mgKOH / g is yet more preferable, and 50 to 80 mgKOH / g is particularly preferable. By setting it to be not less than the lower limit value, the dispersibility tends to be good. By setting it to be not more than the upper limit value, the compatibility with the (A) alkali-soluble resin tends to be good.

[0217] Here, the amine value is represented by the mass of KOH equivalent to the base amount per 1 g of the solid content excluding the solvent in the dispersant sample, and is measured by the following method. Precisely weigh 0.5 to 1.5 g of the dispersant sample into a 100 mL beaker and dissolve it with 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, neutralize and titrate this solution with a 0.1 mol / L HClO4 acetic acid solution. Take the inflection point of the titration pH curve as the titration end point, and calculate the amine value by the following formula. Amine value [mgKOH / g] = (561 × V) / (W × S) 〔However, W represents the weighed amount of the dispersant sample [g], V represents the titration volume at the titration end point [mL], and S represents the solid content concentration of the dispersant sample [mass%].〕

[0218] The weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, still more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 50000 or less, more preferably 20000 or less, and still more preferably 15000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 50000 is preferable, 3000 to 50000 is more preferable, 4000 to 20000 is still more preferable, and 5000 to 15000 is particularly preferable. By setting it to be not less than the lower limit value, the dispersibility tends to be good, and by setting it to be not more than the upper limit value, the viscosity change tends to be less likely to occur.

[0219] As the acrylic dispersant, in addition to the dispersants described above, known dispersants can also be used. For example, the methods described in Japanese Patent Application Laid-Open No. 2013-119568, Japanese Patent Application Laid-Open No. 2017-182092, Japanese Patent Application Laid-Open No. 2017-019937, International Publication No. 2019 / 107020, International Publication No. 2008 / 156148, and Japanese Patent Application Laid-Open No. 2010-256509 can be adopted.

[0220] <(F) Solvent> The photosensitive resin composition of the present invention preferably contains a (F) solvent. By containing the (F) solvent, coating becomes easy. The photosensitive resin composition is used, for example, in a state where (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) an ethylenically unsaturated compound, (D) a colorant, (E) a dispersant, and various other materials used as necessary are dissolved or dispersed in a (F) solvent. As the (F) solvent, an organic solvent is preferable from the viewpoints of dispersibility and coatability.

[0221] As the organic solvent, from the viewpoint of coatability, those having a boiling point of 100 to 300 °C are preferable, and those having a boiling point of 120 to 280 °C are more preferable. Here, the boiling point means the boiling point at a pressure of 1013.25 hPa, and the same applies to the following boiling points.

[0222] Examples of such organic solvents include the organic solvents described below. Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0223] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono - n - butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3 - methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono - n - butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3 - methyl - 3 - methoxybutyl acetate; Glycol diacetates such as ethylene glycol diacetate, 1,3 - butylene glycol diacetate, 1,6 - hexylene glycol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

[0224] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentanol, glycerin, benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

[0225] Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride, amyl chloride; Ether ketones such as methoxymethyl pentanone; Nitriles such as acetonitrile, benzonitrile.

[0226] As commercially available organic solvents, for example, mineral spirit, Varsol #2, Apco #18 solvent, Apco thinner, Socar solvent No.1 and No.2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (「cellosolve」 is a registered trademark. The same shall apply hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all are trade names) can be used. These organic solvents may be used alone or in combination of two or more.

[0227] When forming a partition wall by a photolithography method, it is preferable to select an organic solvent having a boiling point of 100 to 240 °C, more preferably 120 to 200 °C, and even more preferably 120 to 170 °C.

[0228] From the viewpoint of good balance of coatability, surface tension, etc. and relatively high solubility of the constituent components in the photosensitive resin composition, glycol alkyl ether acetates are preferable as the organic solvent. Glycol alkyl ether acetates may be used alone or in combination of two or more. It may be used only with glycol alkyl ether acetates, but other organic solvents may be used in combination. As the organic solvent to be used in combination, glycol monoalkyl ethers are preferable. From the solubility of the constituent components in the photosensitive resin composition, propylene glycol monomethyl ether is more preferable. Glycol monoalkyl ethers have high polarity. If the addition amount is too large, the pigment tends to aggregate, and the storage stability such as an increase in the viscosity of the resulting photosensitive resin composition tends to decrease. Therefore, the ratio of glycol monoalkyl ethers to the total mass of the (F) solvent is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass.

[0229] By using in combination an organic solvent having a boiling point of 150 °C or higher (hereinafter also referred to as "high boiling point solvent"), the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the photosensitive resin composition from being destroyed by rapid drying. Therefore, a high boiling point solvent may be used in combination. For example, it has an effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of a colorant or the like at the tip of a slit nozzle. From the viewpoint of high such an effect, when using a high boiling point solvent in combination, it is preferable to use diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate in combination.

[0230] When using a high-boiling solvent in combination, the content ratio of the high-boiling solvent to the total mass of the (F) solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. By setting it to be not less than the lower limit value, for example, there is a tendency to suppress the precipitation and solidification of the colorant or the like at the tip of the slit nozzle and to cause foreign matter defects. By setting it to be not more than the upper limit value, there is a tendency to suppress the increase in the drying time of the photosensitive resin composition and to suppress problems such as tact failures in the vacuum drying process and pinholes in the pre-baking.

[0231] The high-boiling solvent may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, it is not necessary to separately contain the high-boiling solvent. Preferred high-boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, and triacetin.

[0232] <Other compounding components> In addition to the above-described components, additives such as phosphoric acid compounds, silane coupling agents, surfactants, pigment derivatives, mercapto compounds, and polymerization inhibitors can be appropriately blended in the photosensitive resin composition of the present invention.

[0233] (1) Phosphoric acid compounds The photosensitive resin composition of the present invention may contain a phosphoric acid compound in order to reduce residues and improve adhesion to a substrate. It is presumed that a part of the phosphoric acid compound is adsorbed at the substrate-coating film interface, making it difficult for the pigment component that causes residues to remain on the substrate, and having the effect of reducing residues. As the phosphoric acid compound, those represented by the following formula (g1) are preferred.

[0234]

Chemical formula

[0235] In formula (g1), R 51 represents a hydrogen atom or a methyl group, l represents an integer of 1 to 10, l' represents an integer of 0 to 10, and m represents a number of 1 to 3. R 51 is preferably a methyl group. l is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. l' is preferably 0 to 5, more preferably 0 to 3, even more preferably 0 to 1, and particularly preferably 0. m is preferably 1 to 2. Examples of such phosphoric acid compounds include PM-2 and PM-21 manufactured by Nippon Kayaku Co., Ltd. The phosphoric acid compound may be used alone or in combination of two or more.

[0236] (2) Silane coupling agent The photosensitive resin composition of the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate. As the silane coupling agent, for example, various silane coupling agents such as epoxy-based, (meth)acrylic-based, and amino-based can be used.

[0237] Examples of the silane coupling agent include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, and isocyanatosilanes such as 3-isocyanatopropyltriethoxysilane. Among these, epoxy silane-based silane coupling agents are particularly preferred.

[0238] (3) Surfactant The photosensitive resin composition of the present invention may contain a surfactant in order to improve the coatability. As the surfactant, for example, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. In terms of having little influence on various properties, it is preferable to use a nonionic surfactant, and in terms of coatability, a fluorine-based or silicone-based surfactant is more preferable. Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340 (manufactured by Shin-Etsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar), and FC4430 (manufactured by 3M). One kind of surfactant may be used, or two or more kinds may be used in combination.

[0239] (4) Pigment derivative The photosensitive resin composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability. Examples of the pigment derivative include derivatives of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine. Among these, phthalocyanine-based and quinophthalone-based are preferable. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, and an amide group directly bonded to the pigment skeleton or bonded via, for example, an alkyl group, an aryl group, or a heterocyclic group. Among these, a sulfonic acid group is preferable. A plurality of substituents may be substituted on one pigment skeleton, or a plurality of types of substituents may be substituted.

[0240] Examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, quinophthalone, anthraquinone, quinacridone, diketopyrrolopyrrole, and dioxazine. These may be used alone or in combination of two or more kinds.

[0241] (5) Mercapto compound The photosensitive resin composition of the present invention may contain a mercapto compound as a polymerization accelerator and also for improving the adhesion to a substrate.

[0242] Examples of the mercapto compound include mercapto compounds having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristthioglycolate, butanediol bisthiopropionate, trimethylolpropane tristthiopropionate, trimethylolpropane tristthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristthiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and aliphatic polyfunctional mercapto compounds. These may be used alone or in combination of two or more.

[0243] (6) Polymerization inhibitor From the viewpoint of controlling the shape of the cured product, the photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, since it inhibits radical polymerization in the lower layer of the coating film, it is considered that the taper angle (the angle formed by the support and the cured product in the cross section of the cured product) can be controlled. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferred. From the viewpoint of particularly excellent working environment, etc., hydroquinone monomethyl ether and methylhydroquinone are preferred. The polymerization inhibitor may be used alone or in combination of two or more. (A) When producing an alkali-soluble resin, the alkali-soluble resin (A) may contain a polymerization inhibitor. In that case, the polymerization inhibitor in the resin may be used as the polymerization inhibitor in the present invention, or in addition to the polymerization inhibitor in the resin, the same or different polymerization inhibitor may be added during the production of the photosensitive resin composition.

[0244] <Content ratio of each component in the photosensitive resin composition> (A) The content ratio of the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. Also, it is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 85% by mass is preferred, 5 to 80% by mass is more preferred, 10 to 70% by mass is still more preferred, 20 to 60% by mass is even more preferred, 30 to 60% by mass is still more preferred, and 40 to 60% by mass is particularly preferred. By setting the lower limit value or more, a decrease in the solubility of the unexposed portion in the developer can be suppressed, and development failure can be suppressed. By setting the upper limit value or less, appropriate sensitivity can be maintained, dissolution of the exposed portion by the developer can be suppressed, and a decrease in the sharpness and adhesion of the pattern can be suppressed.

[0245] The content ratio of the alkali-soluble resin (A1) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. Also, it is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 85% by mass is preferable, 5 to 80% by mass is more preferable, 10 to 70% by mass is still more preferable, 20 to 60% by mass is even more preferable, 30 to 60% by mass is still more preferable, and 40 to 60% by mass is particularly preferable. By setting it to be not less than the lower limit value, there is a tendency to suppress fumes. By setting it to be not more than the upper limit value, there is a tendency to maintain appropriate sensitivity and lower the driving voltage during the formation of the organic electroluminescent element.

[0246] (A) The content ratio of the alkali-soluble resin (A1) in the alkali-soluble resin is not particularly limited, but based on 100% by mass of the total mass of the (A) alkali-soluble resin, 10% by mass or more is preferable, 40% by mass or more is more preferable, 70% by mass or more is still more preferable, 80% by mass or more is particularly preferable, and 100% by mass or less is preferable, 95% by mass or less is more preferable. By setting it to be not less than the lower limit value, there is a tendency to suppress fumes. By setting it to be not more than the upper limit value, there is a tendency to lower the driving voltage during the formation of the organic electroluminescent element.

[0247] (B) The content ratio of the photoinitiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. Also, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly preferably 6% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 0.1 to 15% by mass is preferable, 0.5 to 15% by mass is more preferable, 1 to 10% by mass is still more preferable, 2 to 8% by mass is even more preferable, and 3 to 6% by mass is particularly preferable. By setting it to be not less than the lower limit value, there is a tendency to suppress a decrease in sensitivity. By setting it to be not more than the upper limit value, there is a tendency to suppress a decrease in solubility of the unexposed portion in the developer and to suppress development defects.

[0248] (B) When a polymerization accelerator is used together with the photoinitiator, the content ratio of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more based on the total solid content of the photosensitive resin composition of the present invention. Also, it is preferably 10% by mass or less, more preferably 5% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 0.05 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable. Also, the content ratio of the polymerization accelerator is preferably 0.1 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the (B) photoinitiator. By setting the content ratio of the polymerization accelerator to be not less than the lower limit value, there is a tendency to suppress a decrease in sensitivity to the exposure light. By setting it to be not more than the upper limit value, there is a tendency to suppress a decrease in solubility of the unexposed portion in the developer and to suppress development defects. (B) When a sensitizing dye is used together with the photoinitiator, the content ratio of the sensitizing dye is not particularly limited, but from the viewpoint of sensitivity, it is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, based on the total solid content in the photosensitive resin composition.

[0249] (C) The content ratio of the ethylenically unsaturated compound is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, particularly preferably 15% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. Also, it is preferably 40% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 40% by mass is preferable, 1 to 25% by mass is more preferable, 5 to 20% by mass is still more preferable, 10 to 20% by mass is particularly preferable, and 15 to 20% by mass is most preferable. By setting it to be not less than the lower limit value, it is possible to maintain appropriate sensitivity, suppress dissolution by the developer in the exposed area, and also suppress a tendency for deterioration of pattern sharpness and adhesion. By setting it to be not more than the upper limit value, it is possible to suppress an increase in the penetrability of the developer into the exposed area, and it tends to be easy to obtain a good image.

[0250] (C) The content ratio of the (A) alkali-soluble resin with respect to 100 parts by mass of the ethylenically unsaturated compound is not particularly limited, but 50 parts by mass or more is preferable, 100 parts by mass or more is more preferable, 200 parts by mass or more is still more preferable, 250 parts by mass or more is even more preferable, 300 parts by mass or more is particularly preferable. Also, 700 parts by mass or less is preferable, 600 parts by mass or less is more preferable, and 500 parts by mass or less is still more preferable. The above upper and lower limits can be arbitrarily combined. For example, 50 to 700 parts by mass is preferable, 100 to 600 parts by mass is more preferable, 200 to 500 parts by mass is still more preferable, 250 to 500 parts by mass is even more preferable, and 300 to 500 parts by mass is particularly preferable. By setting it to be not less than the lower limit value, it tends to result in an appropriate dissolution and development state without peeling or the like. By setting it to be not more than the upper limit value, it tends to be possible to suppress fumes.

[0251] (C) The content ratio of the (B) photoinitiator with respect to 100 parts by mass of the ethylenically unsaturated compound is not particularly limited, but 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is further preferable, 20 parts by mass or more is particularly preferable. Also, 100 parts by mass or less is preferable, 70 parts by mass or less is more preferable, 40 parts by mass or less is further preferable, 30 parts by mass or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 5 to 100 parts by mass is preferable, 10 to 70 parts by mass is more preferable, 15 to 40 parts by mass is further preferable, 20 to 30 parts by mass is even more preferable. By setting it to be not less than the lower limit value, there is a tendency to suppress fumes. By setting it to be not more than the upper limit value, there is a tendency for good developability.

[0252] When the photosensitive resin composition of the present invention contains a (D) colorant, the content ratio of the (D) colorant is not particularly limited, but 5% by mass or more is preferable with respect to the total solid content of the photosensitive resin composition, 10% by mass or more is more preferable, 15% by mass or more is further preferable, 20% by mass or more is even more preferable. Also, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, 25% by mass or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 5 to 50% by mass is preferable, 10 to 40% by mass is more preferable, 15 to 30% by mass is further preferable, 15 to 25% by mass is particularly preferable. By setting it to be not less than the lower limit value, there is a tendency to ensure light-shielding properties. By setting it to be not more than the upper limit value, the amount of dispersant can be reduced, and there is a tendency to suppress surface roughness.

[0253] (D) When the colorant contains an organic pigment, the content ratio of the organic pigment is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 20% by mass or more, based on the total solid content of the photosensitive resin composition. Also, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 25% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 50% by mass is preferable, 10 to 40% by mass is more preferable, 15 to 30% by mass is still more preferable, and 20 to 30% by mass is particularly preferable. By setting it to be not less than the lower limit value, the light-shielding property tends to be enhanced while suppressing the loss of ultraviolet light necessary for curing. By setting it to be not more than the upper limit value, the driving voltage in the organic electroluminescent element tends to be reduced.

[0254] When the organic pigment contains a black pigment, the content ratio of the black pigment is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 20% by mass or more, based on the total solid content of the photosensitive resin composition. Also, it is preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 2 to 50% by mass is preferable, 3 to 50% by mass is more preferable, 5 to 50% by mass is still more preferable, 10 to 40% by mass is even more preferable, 15 to 30% by mass is still more preferable, 15 to 25% by mass is particularly preferable, and 15 to 20% by mass is most preferable. By setting it to be not less than the lower limit value, the light-shielding property tends to be enhanced. By setting it to be not more than the upper limit value, the driving voltage in the organic electroluminescent element tends to be reduced.

[0255] When the black pigment contains an organic black pigment, the content ratio of the organic black pigment is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 2 to 50% by mass is preferable, 3 to 50% by mass is more preferable, 5 to 50% by mass is still more preferable, 10 to 40% by mass is even more preferable, 15 to 30% by mass is still more preferable, 15 to 25% by mass is particularly preferable, and 15 to 20% by mass is most preferable. By setting the value to be equal to or higher than the lower limit value, the light-shielding property tends to be enhanced. By setting the value to be equal to or lower than the upper limit value, the driving voltage in the organic electroluminescent element tends to be reduced.

[0256] When the black pigment contains an organic black pigment, the content ratio thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 100% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less, based on the total mass of the (D) colorant. The above upper and lower limits can be arbitrarily combined. For example, 5 to 100% by mass is preferable, 10 to 100% by mass is more preferable, 15 to 80% by mass is still more preferable, and 20 to 70% by mass is particularly preferable. By setting the value to be equal to or higher than the lower limit value, the light-shielding property tends to be enhanced. By setting the value to be equal to or lower than the upper limit value, the driving voltage in the organic electroluminescent element tends to be reduced.

[0257] When the photosensitive resin composition of the present invention contains (E) a dispersant, the content ratio of (E) the dispersant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, based on the total solid content of the photosensitive resin composition, and is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and even more preferably 7% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20% by mass is preferable, 2 to 15% by mass is more preferable, 3 to 10% by mass is still more preferable, and 3 to 7% by mass is particularly preferable. By setting it to be not less than the lower limit value, sufficient dispersibility tends to be easily obtained. By setting it to be not more than the upper limit value, surface roughness of the electrode surface tends to be suppressed.

[0258] (D) The content ratio of (E) the dispersant with respect to 100 parts by mass of the colorant is not particularly limited, but 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is still more preferable, and 50 parts by mass or less is preferable, 30 parts by mass or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, 5 to 50 parts by mass is preferable, 10 to 50 parts by mass is more preferable, and 15 to 30 parts by mass is still more preferable. By setting it to be not less than the lower limit value, sufficient dispersibility tends to be easily obtained. By setting it to be not more than the upper limit value, surface roughness of the electrode surface tends to be suppressed.

[0259] When the photosensitive resin composition contains a phosphoric acid compound, its content ratio is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, particularly preferably 1.5% by mass or more, based on the total solid content of the photosensitive resin composition, and is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.0% by mass or less. By setting it to be not less than the lower limit value, the residue in the opening tends to be suppressed. By setting it to be not more than the upper limit value, the composition tends to be less likely to deteriorate during long-term storage.

[0260] When the photosensitive resin composition contains a silane coupling agent, its content ratio is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, 0.1 to 5% by mass is preferable, 0.2 to 3% by mass is more preferable, and 0.4 to 2% by mass is even more preferable. By setting it to be not less than the lower limit value, there is a tendency to sufficiently obtain the effect of improving adhesion. By setting it to be not more than the upper limit value, there is a tendency to suppress a decrease in sensitivity and the remaining of residues after development to cause defects.

[0261] When the photosensitive resin composition contains a surfactant, its content ratio is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, 0.001 to 10% by mass is preferable, 0.005 to 1% by mass is more preferable, 0.01 to 0.5% by mass is even more preferable, and 0.03 to 0.3% by mass is particularly preferable. By setting it to be not less than the lower limit value, there is a tendency for the smoothness and uniformity of the coating film to be easily manifested. By setting it to be not more than the upper limit value, there is a tendency for the smoothness and uniformity of the coating film to be easily manifested and the deterioration of other properties to be suppressed.

[0262] When the photosensitive resin composition contains a polymerization inhibitor, its content ratio is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, not less than 0.0005% by mass is preferable, not less than 0.001% by mass is more preferable, not less than 0.01% by mass is even more preferable, and further, not more than 0.3% by mass is preferable, not more than 0.2% by mass is more preferable, and not more than 0.1% by mass is even more preferable. The above upper and lower limits can be arbitrarily combined. For example, 0.0005 to 0.3% by mass is preferable, 0.001 to 0.2% by mass is more preferable, and 0.01 to 0.1% by mass is even more preferable. By setting it to be not less than the lower limit value, there is a tendency to be able to control the shape of the cured product. By setting it to be not more than the upper limit value, there is a tendency to maintain the required sensitivity.

[0263] When the photosensitive resin composition contains a (F) solvent, its content ratio is set in consideration of the content ratio of the total solid content of the photosensitive resin composition. The content ratio of the total solid content of the photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, based on the total mass of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 5 to 50% by mass is preferable, 10 to 30% by mass is more preferable, and 15 to 25% by mass is still more preferable.

[0264] <Physical properties of the photosensitive resin composition> The optical density (OD) per 1 μm thickness of the coating film obtained by curing the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.7 or more, particularly preferably 0.9 or more, and preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, particularly preferably 1.5 or less. The above upper and lower limits can be arbitrarily combined. For example, 0.2 to 4.0 is preferable, 0.5 to 4.0 is more preferable, 0.5 to 3.0 is still more preferable, 0.5 to 2.0 is even more preferable, 0.7 to 2.0 is still even more preferable, and 0.9 to 1.5 is particularly preferable. By setting the value to be not less than the lower limit value, sufficient light-shielding properties tend to be obtained. By setting the value to be not more than the upper limit value, fume tends to be suppressed.

[0265] The optical density (OD) per 1 μm thickness of the coating film can be obtained by measuring the optical density of the coating film obtained by curing the photosensitive resin composition of the present invention and converting it to the optical density per 1 μm thickness. The coating film can be formed, for example, by applying the photosensitive resin composition onto a support so that the cured thickness is about 0.5 to 1.5 μm and heating and curing it at 230 °C for 20 minutes. The optical density refers to the transmission optical density in which the spectral sensitivity characteristics of the light-receiving part are indicated by ISO visual density in the ISO 5-3 standard. Usually, as the light source, an A light source defined by the CIE (International Commission on Illumination) is used. Examples of the measuring instrument that can be used for measuring the transmission optical density include X-Rite 361T(V) manufactured by Sakata Inx Engineering Co., Ltd.

[0266] <Method for producing photosensitive resin composition> The photosensitive resin composition of the present invention is produced according to a conventional method. For example, it is produced by mixing each component contained in the photosensitive resin composition with a stirrer. (D) The colorant is preferably subjected to a dispersion treatment in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (D) colorant is made into fine particles by the dispersion treatment, the coating properties of the photosensitive resin composition are improved.

[0267] The dispersion treatment is preferably carried out in a system using a combination of (D) colorant, (E) dispersant, and (F) solvent, or a system optionally using a part or all of (A) alkali-soluble resin in combination therewith (hereinafter, the composition obtained by the dispersion treatment is also referred to as a "pigment dispersion liquid"). In particular, when a polymer dispersant is used as the (E) dispersant, thickening over time of the obtained pigment dispersion liquid and photosensitive resin composition is suppressed, that is, it is preferable because of excellent dispersion stability. As the (D) colorant, (A) alkali-soluble resin, (E) dispersant, and solvent that can be used in the pigment dispersion liquid, those described as being usable in the photosensitive resin composition can be preferably employed.

[0268] When the dispersion treatment is carried out on a liquid containing all the components to be blended in the photosensitive resin composition, due to the heat generation during the dispersion treatment, there is a possibility that highly reactive components may be denatured. Therefore, it is preferable to carry out the dispersion treatment in a system containing the (E) dispersant. When dispersing the (D) colorant with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is preferably from 0°C to 100°C, more preferably from room temperature to 80°C. Since the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus, etc., it is adjusted as appropriate. The guideline for dispersion is to control the gloss of the pigment dispersion so that the 20-degree specular glossiness (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300. When the glossiness of the photosensitive resin composition is low, the dispersion treatment is often insufficient and rough pigment (colorant) particles remain, which may lead to insufficient developability, adhesion, resolution, etc. If the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired instead. The dispersion particle size of the pigment dispersed in the pigment dispersion is preferably 0.03 to 0.3 μm. The dispersion particle size can be measured by the dynamic light scattering method.

[0269] Next, the pigment dispersion obtained by the above dispersion treatment is mixed with other components contained in the photosensitive resin composition to obtain a uniform solution or dispersion. In the manufacturing process of the photosensitive resin composition, since fine dust may be mixed in the liquid, it is desirable to filter the obtained photosensitive resin composition with a filter or the like.

[0270] <Use of the photosensitive resin composition> The photosensitive resin composition of the present invention can be used, for example, as a resin composition for forming a black matrix, an insulating film, or a partition wall, and is suitable as a resin composition for forming a partition wall.

[0271] [Cured product] By curing the photosensitive resin composition of the present invention, the cured product of the present invention can be obtained. The cured product of the present invention can be formed in any shape on an arbitrary support. The cured product obtained by curing the photosensitive resin composition of the present invention can be used, for example, as a black matrix, an insulating film, or a partition wall, and can be preferably used as a partition wall.

[0272] The thickness of the cured product is preferably 0.5 μm or more, more preferably 0.7 μm or more, still more preferably 0.9 μm or more, and preferably 15 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The above upper and lower limits can be arbitrarily combined. For example, 0.5 to 15 μm is preferable, 0.7 to 10 μm is more preferable, and 0.9 to 5 μm is still more preferable.

[0273] From the viewpoint of light shielding property, the optical density (OD) per 1 μm of the thickness of the cured product of the present invention is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and particularly preferably 0.9 or more. Also, it is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, and particularly preferably 1.5 or less. The above upper and lower limits can be arbitrarily combined. For example, 0.2 to 4.0 is preferable, 0.5 to 4.0 is more preferable, 0.5 to 3.0 is still more preferable, 0.5 to 2.0 is even more preferable, 0.7 to 2.0 is still more preferable, and 0.9 to 1.5 is particularly preferable.

[0274] Next, the cured product of the present invention will be described according to its production method.

[0275] (1) Support As the support for forming the cured product, as long as it has appropriate strength, its material is not particularly limited. Although a substrate is mainly used, examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic resin, and various glasses. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred. In addition, a transparent electrode such as ITO or IZO, or a metal electrode such as silver, gold, platinum, aluminum, or magnesium may be formed on the surface of the substrate. In addition to the above-described substrates, it is also possible to form on the TFT array.

[0276] For the support, in order to improve surface physical properties such as adhesiveness, if necessary, for example, corona discharge treatment, ozone treatment, or thin film formation treatment of various resins such as silane coupling agents and urethane resins may be performed. The thickness of the support is preferably in the range of 0.05 to 10 mm, more preferably in the range of 0.1 to 7 mm. When performing thin film formation treatment of various resins, the thickness is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 5 μm.

[0277] On the support on which the cured product is to be provided, the photosensitive resin composition is supplied in a film shape or a pattern shape by a method such as coating, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method in which exposure and development are performed. Thereafter, if necessary, post-exposure or heat curing treatment is performed to form a cured product on the substrate.

[0278] (2) Supply method to the support The photosensitive resin composition of the present invention is preferably supplied onto a support in a state of being dissolved or dispersed in a solvent. As the supply method, a conventionally known method, for example, a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, or a spray coat method can be used. Further, for example, it may be supplied in a pattern by an inkjet method or a printing method. According to the die coat method, the amount of the coating solution used is significantly reduced, and there is no influence of mist or the like adhering when using the spin coat method, and foreign matter generation is suppressed. Therefore, it is preferable from a comprehensive viewpoint.

[0279] The coating amount of the photosensitive resin composition varies depending on the application, but as a dry film thickness, it is preferably applied so as to be 0.5 μm to 10 μm, more preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. It is important that the dry film thickness or the height of the finally formed cured product is uniform over the entire area of the support. By reducing the variation, the light-shielding property in the support becomes uniform, and when used as a partition wall, a light-emitting layer can be formed uniformly, and display defects during light emission can be suppressed.

[0280] When batch-forming cured products having different heights by a photolithography method using the photosensitive resin composition of the present invention, the heights of the finally formed cured products will be different.

[0281] (3) Drying method After supplying the photosensitive resin composition onto the support, drying is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. A vacuum drying method in which drying is performed in a vacuum chamber without increasing the temperature may be combined.

[0282] The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, etc. The drying time is preferably selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C to 130 ° C, and more preferably selected in the range of 30 seconds to 3 minutes at a temperature of 50 ° C to 110 ° C, according to the type of the solvent component, the performance of the dryer used, etc.

[0283] (4) Exposure method Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive resin composition and irradiating a light source of ultraviolet or visible light through this mask pattern. When performing exposure using an exposure mask, it may also be performed by a method of bringing the exposure mask close to the coating film of the photosensitive resin composition, or by a method of disposing the exposure mask at a position away from the coating film of the photosensitive resin composition and projecting the exposure light through the exposure mask. A scanning exposure method using laser light without a mask pattern may also be used. If necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, it may be performed under a deoxygenated atmosphere, or exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

[0284] When simultaneously forming cured products with different heights by photolithography, for example, an exposure mask having an opening with a lower average light transmittance (intermediate transmission opening) with respect to an opening with the highest average light transmittance (complete transmission opening) is used as a light-shielding portion (light transmittance 0%) and a plurality of openings. By this method, a difference in the residual film rate is caused by the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the exposure amount. As a method for creating the intermediate transmission opening, for example, a method using a matrix-shaped light-shielding pattern having minute polygonal light-shielding units is known. As an absorber, for example, a method of controlling the light transmittance by a film of a chromium-based, molybdenum-based, tungsten-based, or silicone-based material is known.

[0285] The light source used for exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When irradiating light of a specific wavelength for use, an optical filter can also be used.

[0286] As the optical filter, for example, a type capable of controlling the light transmittance at the exposure wavelength with a thin film may be used. In that case, examples of the material include Cr compounds (oxides, nitrides, oxynitrides, fluorides, etc. of Cr), MoSi, Si, W, and Al.

[0287] The exposure amount is not particularly limited, but preferably 1 mJ / cm 2 or more, more preferably 5 mJ / cm 2 or more, still more preferably 10 mJ / cm 2 or more, and preferably 300 mJ / cm 2 or less, more preferably 200 mJ / cm 2 or less, still more preferably 150 mJ / cm 2 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 300 mJ / cm 2 is preferable, 5 to 200 mJ / cm 2 is more preferable, and 10 to 150 mJ / cm 2 is still more preferable. The above upper and lower limits can be arbitrarily combined. For example, 10 to 500 μm or more is preferable, 50 to 400 μm is more preferable, and 75 to 300 μm is still more preferable.

[0288] (5) Development method After performing the above exposure, a cured product can be formed in a predetermined pattern on the support by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0289] Examples of the alkaline compound include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, etc., and organic alkaline compounds such as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline, etc. These alkaline compounds may be used alone or in combination of two or more kinds.

[0290] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, etc.; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters, etc.; and amphoteric surfactants such as alkyl betaines, amino acids, etc. The surfactant may be used alone or in combination of two or more kinds.

[0291] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol. These organic solvents may be used in combination of two or more kinds. The organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.

[0292] There are no particular restrictions on the conditions for the development process. The development temperature is preferably 10 to 50°C, more preferably 15 to 45°C, and even more preferably 20 to 40°C. The development method can be, for example, dip development, spray development, brush development, or ultrasonic development.

[0293] (6) Post-exposure and heat curing treatment After development, the substrate may be post-exposed by a method similar to the above exposure method if necessary. After development or post-exposure, heat curing treatment (also referred to as baking) may be performed. The heat curing treatment conditions are preferably a temperature of 100°C to 280°C, more preferably 150°C to 250°C, and preferably a time of 5 minutes to 60 minutes.

[0294] [Partition wall] The photosensitive resin composition of the present invention can be suitably used for forming partition walls. In particular, it can be suitably used for forming partition walls for partitioning organic layers of organic electroluminescent elements or for partitioning pixel portions in color filters containing light-emitting nanocrystalline particles.

[0295] Specifically, the partition wall of the present invention is composed of the cured product of the present invention described above. On the support on which the partition wall is to be provided, the photosensitive resin composition of the present invention is supplied in a film or pattern form by a method such as coating, and the solvent is dried. Subsequently, patterning is performed by a method such as photolithography for performing exposure and development. Thereafter, if necessary, post-exposure or heat curing treatment is performed to form a partition wall on the support. Specific methods for the supply method, drying method, exposure method, development method, post-exposure treatment, and heat curing treatment of the photosensitive resin composition include the various methods and treatment methods exemplified in the description of the cured product of the present invention described above.

[0296] When the present invention is used as a partition wall, the size, shape, etc. are appropriately adjusted according to the specifications of the organic electroluminescent element to which it is applied. For example, the thickness of the partition wall is preferably about 0.5 to 10 μm. Further, the optical density (OD) per 1 μm thickness of the partition wall is the same as the value of the optical density per 1 μm thickness of the coating film obtained by curing the photosensitive resin composition of the present invention. The thickness of the partition wall is measured by a step, surface roughness, and fine shape measuring device, a scanning white light interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, or an electron microscope.

[0297] [Organic electroluminescent element] The organic electroluminescent element of the present invention includes a cured product formed of the photosensitive resin composition of the present invention, for example, a partition wall. For example, using a substrate provided with a partition wall pattern manufactured by the method described above, various organic electroluminescent elements are manufactured. The method for forming the organic electroluminescent element is not particularly limited, but preferably, after forming a pattern of the partition wall on the substrate by the method described above, a functional material is sublimated in a vacuum state and deposited in a region surrounded by the partition wall on the substrate to form a film. The organic electroluminescent element is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an inkjet printing method. Examples of the organic layer used for the organic electroluminescent element include a hole injection layer, a hole transport layer, or an organic layer used for the hole transport layer on the hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396.

[0298] Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type. In the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated as a reflection layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall. Examples of the light-emitting layer include an organic electroluminescent layer as described in JP-A-2009-146691 and Japanese Patent No. 5734681. Quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[0299] The layer structure is not limited to this. For example, each of the hole transport layer and the electron transport layer may have a laminated structure composed of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is preferably 1 to 500 nm from the viewpoints of luminous efficiency and luminance.

[0300] The organic electroluminescent element may be formed by separating each RGB color for each opening, or two or more colors may be laminated in one opening. From the viewpoint of improving reliability, the organic electroluminescent element may be provided with a sealing layer. The sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and reducing the luminous efficiency. From the viewpoint of improving the light extraction efficiency, the organic electroluminescent element may be provided with a low-reflection film at the interface with air. By disposing the low-reflection film at the interface between air and the element, it is expected to reduce the refractive index gap and suppress reflection at the interface. For such a low-reflection film, for example, a moth-eye structure and a multi-layer film technology can be applied.

[0301] When the organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light of the light-emitting layer of a certain pixel from leaking to other pixels. Further, when the electrode or the like is made of metal, it is necessary to prevent a decrease in image quality due to reflection of external light. Therefore, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent element. In the organic electroluminescent element, since it is necessary to provide electrodes on the upper and lower surfaces of the partition walls, from the viewpoint of insulation, the partition walls are preferably high-resistance and low-dielectric constant. Therefore, when a colorant is used to impart light-shielding properties to the partition walls, it is preferable to use the organic pigment having high resistance and low dielectric constant.

[0302] [Color Filter] The color filter of the present invention is a color filter including luminescent nanocrystal particles and having the partition walls of the present invention. In the color filter of the present invention, the partition walls are for partitioning pixel portions in a color filter including luminescent nanocrystal particles, and are used to form pixels by discharging and drying ink in the partitioned regions.

[0303] The color filter including luminescent nanocrystal particles is not particularly limited as long as it has the partition walls of the present invention composed of the cured product of the present invention, and examples include those in which pixels are formed in regions partitioned by the partition walls of the present invention.

[0304] FIG. 1 is a schematic cross-sectional view of an example of the color filter of the present invention. As shown in FIG. 1, the color filter 100 includes a substrate 10, partition walls 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50. The partition walls 20 are the partition walls of the present invention. The red pixel 30, the green pixel 40, and the blue pixel 50 are arranged in a lattice pattern so as to repeat in this order. The partition walls 20 are provided between these adjacent pixels. In other words, these adjacent pixels are partitioned by the partition walls 20.

[0305] The red pixel 30 contains red-luminescent nanocrystal particles 2, and the green pixel 40 contains green-luminescent nanocrystal particles 1. The blue pixel 50 is a pixel that transmits blue light from a light source.

[0306] These luminescent nanocrystal particles are nanosized crystals that absorb excitation light and emit fluorescence or phosphorescence, and are, for example, crystals having a maximum particle diameter of 100 nm or less measured by a transmission electron microscope or a scanning electron microscope.

[0307] Luminescent nanocrystal particles can emit light (fluorescence or phosphorescence) with a wavelength different from the absorbed wavelength by absorbing light of a predetermined wavelength. For example, the red luminescent nanocrystal particles 2 emit light (red light) having an emission peak wavelength in the range of 605 to 665 nm. Also, for example, the green luminescent nanocrystal particles 1 emit light (green light) having an emission peak wavelength in the range of 500 to 560 nm.

[0308] According to the solution of the Schrödinger wave equation of the well-type potential model, the wavelength (emission color) of the light emitted by the luminescent nanocrystal particles depends on the size (e.g., particle diameter) of the luminescent nanocrystal particles, but also depends on the energy gap of the luminescent nanocrystal particles. Therefore, the emission color can be selected by changing the constituent material and size of the luminescent nanocrystal particles to be used. Examples of the luminescent nanocrystal particles include quantum dots.

[0309] The method for manufacturing a color filter containing luminescent nanocrystal particles is not particularly limited, but examples include a method of preparing a substrate provided with partition walls composed of the cured product of the present invention and forming a layer containing luminescent nanocrystal particles in the regions partitioned by the partition walls. The method for forming the layer containing luminescent nanocrystal particles is not particularly limited, but for example, it can be manufactured by a method of selectively attaching an ink composition containing luminescent nanocrystal particles by an inkjet method and curing the ink composition by irradiation with active energy rays or heating.

[0310] [Image display device] The image display device of the present invention includes the partition walls of the present invention. Examples of the image display device of the present invention include an organic EL display device having the organic electroluminescent element of the present invention and an image display device provided with the color filter of the present invention. The organic EL display device is not particularly limited with respect to the type and structure of the image display device as long as it includes the above-described organic electroluminescent element. For example, it can be assembled according to a conventional method using an active drive type organic electroluminescent element. For example, it can be formed by a method as described in "Organic EL Display" (published by Ohmsha, Ltd. on August 20, 2004, written by Seishi Tokito, Chihaya Adachi, and Hideyuki Murata). For example, an organic electroluminescent element that emits white light and a color filter may be combined to display an image, or organic electroluminescent elements having different emission colors such as RGB may be combined to display an image. Examples of the type of the image display device provided with the color filter of the present invention include a liquid crystal display device and an image display device including an organic electroluminescent element. Examples of the liquid crystal display device include those including a light source provided with a blue LED and a liquid crystal layer provided with an electrode for controlling the blue light emitted from the light source for each pixel portion. Examples of the image display device including an organic electroluminescent element include those in which an organic electroluminescent element that emits blue light is arranged at a position corresponding to each pixel portion of the color filter. For example, the method described in Japanese Patent Application Laid-Open No. 2019-87746 is included.

Example

[0311] Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The constituent components of the photosensitive resin composition used in the following examples and comparative examples are as follows.

[0312] <Synthesis Example 1: Alkali-Soluble Resin-I>

[0313]

Chemical Formula

[0314] 100 parts by mass of an epoxy compound (epoxy equivalent: 273) having a repeating unit represented by the above formula, 26.42 parts by mass of acrylic acid, 2.53 parts by mass of triphenylphosphine, 0.0632 parts by mass of 4-methoxyphenol, and 84.28 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred. Next, 6.84 parts by mass of benzene-1,2,4-tricarboxylic acid-1,2-anhydride and 48.98 parts by mass of propylene glycol monomethyl ether acetate were further added and reacted. The weight average molecular weight Mw of the alkali-soluble resin-I thus obtained was 2112, and the acid value was 27.2 mgKOH / g.

[0315] <Epoxy acrylate compound I>

[0316]

Chemical formula

[0317] An epoxy compound having the above structure and acrylic acid equivalent to the epoxy group of this epoxy compound were charged into a reaction vessel, and heated and stirred at 105 °C until the acid value reached 5.0 mgKOH / g or less. It took 14 hours until the acid value reached the target, and epoxy acrylate compound I was obtained. Epoxy acrylate compound I corresponds to the reaction product (intermediate (a0)) of component (a1) and component (a2).

[0318] <Alkali-soluble resins-II to VI> The raw materials described in Table 1 were charged into a reaction vessel at the molar ratios described in Table 1, and heated and stirred at 105 °C to obtain alkali-soluble resins-II to VI. Alkali-soluble resins-II to VI correspond to (A1) alkali-soluble resins.

[0319] <Alkali-soluble resin-VII> "KBR-101" manufactured by KISCO. A resin having a fluorene bisphenol skeleton. Weight average molecular weight 4386, acid value 91 mgKOH / g. Alkali-soluble resin-VII does not correspond to (A1) alkali-soluble resins.

[0320] <Alkali-soluble resin-VIII> "KBR-201" manufactured by KISCO. A resin having a fluorene bisphenol skeleton. Weight average molecular weight 5150, acid value 112 mg KOH / g. Alkali-soluble resin-VIII does not correspond to (A1) alkali-soluble resin. Table 1 shows the molar ratios of the raw materials of alkali-soluble resin-VII and alkali-soluble resin-VIII respectively.

[0321]

Table 1

[0322] The abbreviations in Table 1 have the following meanings. TMA: Benzene-1,2,4-tricarboxylic acid-1,2-anhydride (trimellitic anhydride); corresponds to component (a3). HTMA: Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (HTMA); corresponds to component (a3). BPDA: Biphenyltetracarboxylic dianhydride; corresponds to component (a4). THPA: Tetrahydrophthalic anhydride; does not correspond to components (a3) and (a4).

[0323] <Colorant-I> "Irgaphor® Black S 0100 CF" manufactured by BASF (a compound having the chemical structure represented by the following formula (D2)).

[0324]

Chemical formula

[0325] <Dispersant-I> A block copolymer composed of a B block containing a repeating unit having a lyophilic group and an A block containing a repeating unit having a tertiary or quaternary amino group.

[0326] <Solvent-I> PGMEA: Propylene glycol monomethyl ether acetate. <Solvent - II> MB: 3 - Methoxy - 1 - butanol.

[0327] <Photoinitiator - I> An oxime ester - type photoinitiator having the following chemical structure.

[0328]

Chem.

[0329] <Ethylenically Unsaturated Compound - I> "DPHA" manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

[0330] <Surfactant - I> "Megafac F - 559" manufactured by DIC Corporation.

[0331] <Additive - I> "PM21" manufactured by Nippon Kayaku Co., Ltd., a phosphoric acid - based compound represented by the following formula (m is about 1.5).

Chem.

[0332] <Surfactant - II> "PM2" manufactured by Nippon Kayaku Co., Ltd., a phosphoric acid - based compound represented by the following formula (m is about 1.5).

Chem.

[0333] <Preparation of Pigment Dispersion 1> The pigment, dispersant, alkali-soluble resin, and solvent described in Table 2 were mixed so as to have the mass ratios described in Table 1. Beads were added to this mixed solution, and dispersion treatment was performed at 25 to 45 °C for 3 hours using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that of the dispersion liquid was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare Pigment Dispersion Liquid 1. Note that the amount of the solvent in Table 2 includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[0334]

Table 2

[0335] [Examples 1 to 10, Comparative Examples 1, 2] To Pigment Dispersion Liquid 1, each component was added so that the solid content ratio of each component in the total solid content became the values described in Tables 3 and 4. Further, a solvent was added so that PGMEA / MB = 80 / 20 and the total solid content ratio became 17% by mass, and stirring and dissolution were performed to prepare the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2.

[0336] Regarding the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2, the unit OD value and fume were evaluated by the following evaluation methods. The evaluation results are shown in Tables 3 and 4.

[0337] <Measurement of optical density per 1 μm thickness (unit OD value)> The optical density per 1 μm thickness (unit OD value) was measured by the following procedure. Using a spin coater on a glass substrate, the photosensitive resin composition was applied so as to have a thickness of 1.5 μm after heat curing (firing). Thereafter, drying treatment was performed for 60 seconds using a vacuum dryer. Subsequently, heat drying was performed for 100 seconds on a hot plate heated to 100 °C. The obtained coating film was exposed without using a photomask. Using a mirror projection type exposure machine (MPA-600FA) manufactured by Canon, the exposure amount was 80 mJ / cm 2Exposure was carried out for 20 seconds so as to achieve this. The lamp output was 500 mW / cm 2 Subsequently, using a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation), shower development was performed at 24°C with a water pressure of 0.05 MPa. After that, the developer solution was rinsed with pure water to stop the development, and washing was carried out for 10 seconds with a water wash spray. The shower development time was made the same as the shower development time when preparing the residue evaluation substrate. Subsequently, heating and curing were performed in an oven at 230°C for 30 minutes to obtain the resist-coated substrate 1. The optical density (OD value) of the coating film of the obtained resist-coated substrate 1 was measured using a 361T(V) transmission densitometer manufactured by X-Rite (color temperature of the illumination light source: approximately 2850 K (equivalent to CIE standard light source A), spectral sensitivity characteristics of the light receiving part: ISO Visual density according to ISO 5-3 standard). The thickness of the coating film was measured using a non-contact surface and layer cross-sectional shape measurement system VertScan(R) 2.0 manufactured by Rhodamine Systems Co., Ltd. From the optical density (OD value) and the thickness of the coating film, the optical density per unit thickness (1 μm) (unit OD value) was calculated. Note that the OD value is a numerical value indicating the light-shielding ability, and the larger the numerical value, the higher the light-shielding property.

[0338] <Fabrication of Substrate for Fume Measurement> The substrate for fume evaluation was fabricated according to the following procedure. Using a spin coater on a glass substrate, the photosensitive resin composition was applied so as to have a thickness of 1.5 μm after heat curing (firing). Subsequently, drying treatment was performed for 60 seconds with a vacuum dryer. Subsequently, heating and drying were carried out for 100 seconds on a hot plate heated to 100°C. Exposure was carried out on the obtained coating film without using an exposure mask. As the irradiation light source, a mirror projection type exposure machine (MPA-600FA) manufactured by Canon was used, and exposure was carried out for 20 seconds so that the exposure amount was 80 mJ / cm 2 Subsequently, using a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation), shower development was performed at 24°C with a water pressure of 0.05 MPa. After that, the developer solution was rinsed with pure water to stop the development, and washing was carried out for 10 seconds with a water wash spray. The shower development time was made the same as the shower development time when preparing the residue evaluation substrate. Subsequently, heating and curing were performed in an oven at 230°C for 30 minutes to obtain the resist-coated substrate 1. 2 Subsequently, using a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation), shower development was performed at 24°C with a water pressure of 0.05 MPa. After that, the developer solution was rinsed with pure water to stop the development, and washing was carried out for 10 seconds with a water wash spray. The shower development time was made the same as the shower development time when preparing the residue evaluation substrate. Subsequently, heating and curing were performed in an oven at 230°C for 30 minutes to obtain the resist-coated substrate 1. Subsequently, a developer composed of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant ("A-60" manufactured by Kao Corporation) was used. After performing shower development at a water pressure of 0.05 MPa at 24°C, the developer was rinsed with pure water to stop the development, and then washed with a water spray for 10 seconds. The shower development time was the same as the shower development time when preparing the residue evaluation substrate. For each example and comparative example, a substrate for fume measurement with a cured film of the photosensitive colored resin composition was obtained.

[0339] <Fume Evaluation> The substrate for fume measurement was cut into a size of 20 mm × 6 mm with a glass cutter, and two pieces were prepared for each example and comparative example. The prepared substrates for fume measurement were analyzed by GC (Agilent Technologies, product name "8890") and MS (JEOL, product name "JMS-Q1500") for the fumes generated when heated in a TG heating furnace (manufactured by NETZSCH, product name "STA 2500 Regulus") at 230°C for 30 minutes in two pieces each. The sum of the detected peak areas was normalized with the result of Example 1 as 100%, and for each example and comparative example, the fume amount (%) relative to Example 1 was calculated and evaluated according to the following criteria. The smaller the numerical value of the fume amount, the less fume and the better it is. (Fume Evaluation Criteria) A: The fume amount is 80% or less. B: The fume amount is more than 80% and 120% or less. C: The fume amount is more than 120%.

[0340]

Table 3

[0341]

Table 4

[0342] From the results of Examples 1 to 10 in Tables 3 and 4 and Comparative Examples 1 and 2, it was found that the use of (A1) an alkali-soluble resin reduces the amount of fumes during firing. (A1) The alkali-soluble resin has side chains derived from tricarboxylic acids (anhydrides) such as trimellitic acid (anhydride) and hydrogenated trimellitic acid (anhydride) as polybasic acids (anhydrides). Compared with the side chains derived from dicarboxylic acids (anhydrides), an increase in the number of carboxylic acid groups increases the molecular weight or raises the boiling point, making it less likely to thermally decompose during firing. It is considered that the inclusion of such (A1) an alkali-soluble resin in the photosensitive resin composition reduces the generation of fumes during firing. Also, from the difference between Example 1 and Examples 2 to 5, it was found that by changing the molar ratio of component (a3) / component (a4), fume generation can be further suppressed. In particular, when the component (a3) / component (a4) is small, it is presumed that the amount of component (a3) decreases, resulting in fewer decomposition products and further suppression of the fume area.

[0343] For the photosensitive resin compositions of Examples 1 to 7, the residue was evaluated by the following evaluation method. The evaluation results are shown in Table 5.

[0344] <Preparation of Residue Evaluation Substrate> The residue evaluation substrate was prepared by the following procedure. Using a spin coater on a glass substrate, the photosensitive resin composition was applied so as to have a thickness of 1.5 μm after heat curing (firing). Then, it was dried in a vacuum dryer for 60 seconds. Subsequently, it was heated and dried on a hot plate heated to 100 °C for 100 seconds. The obtained coating film was exposed using an exposure mask. As the irradiation light source, a mirror projection type exposure machine (MPA-600FA) manufactured by Canon was used, and exposure was performed for 20 seconds so that the exposure amount was 80 mJ / cm 2 The lamp output was 500 mW / cm 2 A mask having a grid-shaped opening (having a 50 μm square covering portion and a plurality of the covering portions via 50 μm exposure portions) was used as the photomask. Subsequently, a developer composed of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant ("A-60" manufactured by Kao Corporation) was used. After performing shower development at 24°C with a water pressure of 0.05 MPa, the developer was rinsed with pure water to stop the development, and then washed with a water spray for 10 seconds. The shower development time was set to 1.6 times the time required for dissolving and removing the unexposed portion of the coating film. The portion corresponding to the square light-shielding portion was exposed with the ITO substrate because the photosensitive resin composition flowed after development, and a hole portion was formed. Subsequently, by heating and curing at 230°C for 30 minutes in an oven, a residue evaluation substrate with a cured film of the photosensitive resin composition was obtained.

[0345] <Fabrication of Residue Evaluation Substrate> The 50-μm hole portion of the residue evaluation substrate was observed under the dark field of an optical microscope, and the number of residues was counted. The calculated number of residues was determined as follows. A indicates that the number of residues is the least and is good. Note that the residues are related to the exposure sensitivity of the resist and its solubility in the developer, and the fewer the residues, the better. A: The number of residues is 10 or less. B: The number of residues is more than 10 and 150 or less. C: The number of residues is more than 150.

[0346]

Table 5

[0347] From the results of Examples 1 to 5 and Examples 6 and 7 in Table 5, it was found that the alkali-soluble resins II to IX tend to have many residues in the pixels due to the hydrophobicity of the fluorene skeleton. However, by using Additives I and II, while reducing the amount of fumes, the solubility of the residues is improved and the number of residues is decreased. This is presumably because since the photosensitive resin compositions of Examples 6 and 7 contain a phosphoric acid-based compound, a part of the phosphoric acid-based compound is adsorbed on the substrate and coating film interface, making it difficult for the colorant causing the residues to remain on the substrate.

Explanation of Symbols

[0348] 1 Green light-emitting nanocrystalline particles 2 Red light-emitting nanocrystal particles 10 Substrate 20 Partition wall 30 Red pixel 40 Green pixel 50 Blue pixel 100 Color filter

Claims

Claim 1 A photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound, wherein the (A) alkali-soluble resin contains an alkali-soluble resin (A1) which is a reaction product of the following component (a1) and the following component (a2), the following component (a3), and the following component (a4), and is characterized by this, a photosensitive resin composition. Component (a1): At least one selected from the group consisting of an epoxy compound represented by the following formula (1) and a compound in which a substituent is bonded to the benzene ring in the epoxy compound. Component (a2): At least one selected from the group consisting of an α,β-unsaturated monocarboxylic acid and an α,β-unsaturated monocarboxylic acid ester having a carboxy group. Component (a3): At least one selected from the group consisting of tricarboxylic acids and their anhydrides. Component (a4): At least one selected from the group consisting of tetracarboxylic acids and their anhydrides. 【Chemical Formula 1】 (wherein X represents O, S, C(=O) or a single bond, and G １ and G ２ each independently represents an alkylene group having 1 to 4 carbon atoms, n1 and n2 each independently represents an integer of 0 to 10, and when n1 is 2 or more, a plurality of G １ may be the same or different from each other, and when n2 is 2 or more, a plurality of G ２ may be the same or different from each other.) Claim 2 A photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound, wherein the (A) alkali-soluble resin contains an alkali-soluble resin (A1) having two or more partial structures represented by the following formula (a-1-1), one or more partial structures represented by the following formula (a-2), and one or more partial structures represented by the following formula (a-3), and is characterized by this, a photosensitive resin composition. 【Chemical 2】 (wherein, X represents O, S, C(=O) or a single bond, G １ and G ２ each independently represents an alkylene group having 1 to 4 carbon atoms, n1 and n2 each independently represents an integer of 0 to 10, and when n1 is 2 or more, a plurality of G １ may be the same or different from each other, and when n2 is 2 or more, a plurality of G ２ may be the same or different from each other. R １Ａ , R １Ｂ , R １Ｃ , R ２Ａ , R ２Ｂ and R ２Ｃ each independently represents a hydrogen atom or a substituent. R ３ represents a residue derived from a tricarboxylic acid. R ４ represents a residue derived from a tetracarboxylic acid. * represents a bond.) Claim 3 The photosensitive resin composition according to claim 1, wherein the molar ratio ((a3) / (a4)) of the component (a3) to the component (a4) is 0.05 to 0.

70. Claim 4 The photosensitive resin composition according to claim 1, wherein the component (a3) is at least one selected from the group consisting of benzenetricarboxylic acid, its anhydride, cyclohexanetricarboxylic acid, and its anhydride. Claim 5 The photosensitive resin composition according to any one of claims 1 to 4, wherein the content ratio of the alkali-soluble resin (A1) is 10% by mass or more and 95% by mass or less based on the total mass of the (A) alkali-soluble resin. Claim 6 The photosensitive resin composition according to any one of claims 1 to 4, wherein the content ratio of the (A) alkali-soluble resin is 100 parts by mass or more with respect to 100 parts by mass of the (C) ethylenically unsaturated compound. Claim 7 The photosensitive resin composition according to any one of claims 1 to 4, further containing (D) a colorant. Claim 8 The photosensitive resin composition according to claim 7, wherein the (D) colorant contains an organic pigment.

9. The photosensitive resin composition according to claim 8, wherein the organic pigment contains an organic black pigment.

10. The photosensitive resin composition according to claim 9, wherein the organic black pigment contains a benzodifuranone-based organic black pigment.

11. The photosensitive resin composition according to claim 10, wherein the benzodifuranone-based organic black pigment contains at least one organic black pigment selected from the group consisting of a compound represented by the following formula (D-1-1), a geometric isomer thereof, a salt thereof, and a salt of the geometric isomer. 【Chemical Formula 3】 (wherein, R ６１１ and R ６１６ each independently represents a hydrogen atom, CH ３ , CF ３ , a fluorine atom or a chlorine atom; R ６１２ 、R ６１３ 、R ６１４ 、R ６１５ 、R ６１７ 、R ６１８ 、R ６１９ and R ６２０ are each independently a hydrogen atom, a halogen atom, R ６２１ , COOH, COOR ６２１ , COO － , CONH ２ , CONHR ６１１ , CONR ６２１ R ６２２ , CN, OH, OR ６２１ , COCR ６２１ , OOCNH ２ , OOCNHR ６２１ , OOCNR ６２１ R ６２２ , NO ２ , NH ２ , NHR ６２１ , NR ６２１ R ６２２ , NHCOR ６２２ , NR ６２１ COR ６２２ , N = CH ２ , N = CHR ６２１ , N = CR ６２１ R ６２２ , SH, SR ６２１ , SOR ６２１ , SO ２ R ６２１ , SO ３ R ６２１ , SO ３ , SOH, SO ３ － , SO ２ NH ２ , SO ２ , SONHR ６２１ or SO ２ , SONR ６２１ R ６２２ represents; R ６１２ and R ６１３ , R ６１３ and R ６１４ , R ６１４ and R ６１５ , R ６１７ and R ６１８ , R ６１８ and R ６１９ , and R ６１９ and R ６２０ At least one combination selected from the group consisting of is directly bonded to each other or may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR ６２１ bridge; R ６２１ and R ６２２ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms. )

12. The photosensitive resin composition according to claim 7, wherein the content ratio of the (D) colorant is 10% by mass or more based on the total solid content of the photosensitive resin composition.

13. The photosensitive resin composition according to claim 7, further comprising a phosphoric acid compound represented by the following formula (g1). [Chemical Formula 4] (wherein, R ５１ represents a hydrogen atom or a methyl group, l represents an integer of 1 to 10, l' represents an integer of 0 to 10, and m represents a number of 1 to 3.)

14. The photosensitive resin composition according to any one of claims 1 to 4, which is for forming a partition wall.

15. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 4.

16. A partition wall composed of the cured product according to claim 15.

17. An organic electroluminescent element including the partition wall according to claim 16.

18. A color filter containing light-emitting nanocrystalline particles, including the partition wall according to claim 16.

19. An image display device including the partition wall according to claim 16.

Images