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

Abstract

To provide a photosensitive resin composition that has excellent gas barrier performance against outgassing released from an overcoat layer during heating, and is excellent in developability, especially dissolution time in a developing solution.SOLUTION: A photosensitive resin composition comprises (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, wherein the alkali-soluble resin (b) contains an alkali-soluble resin (b-1) having an isocyanurate ring, a (meth)acryloyloxy group, a carboxyl group, and a urethane bond.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 device, and an image display device. [Background technology]

[0002] Liquid crystal displays (LCDs) utilize the property that liquid crystal molecules change their alignment when a voltage is applied to the liquid crystal, while many of the components that make up an LCD cell are formed using methods that utilize photosensitive compositions, such as photolithography. This photosensitive composition is likely to find wider application in the future because it is easy to form fine structures and is easy to process on substrates for large screens.

[0003] On the other hand, image display devices including organic electroluminescence (also called organic EL) devices are attracting attention as the next generation of flat panel displays (FPDs) because they offer excellent visibility such as contrast and viewing angle, responsiveness, and the ability to reduce power consumption, thinness and weight, and 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 is light-transmitting. An image display device displays images by driving a panel in which an organic electroluminescent element is arranged for each pixel.

[0004] Conventionally, such organic electroluminescent devices are manufactured by forming partition walls (banks) on a substrate, and then laminating a light-emitting layer or various functional layers in the area surrounded by the partition walls. The deposition method, in which a material is sublimated in a vacuum and deposited on a substrate, is the main method for depositing a film such as an emitting layer in the region surrounded by the partition wall. In recent years, wet process deposition methods such as casting, spin coating, and inkjet printing have been attracting attention.

[0005] As a display device having an organic electroluminescent element, for example, Japanese Patent Publication No. 2013-125746 describes a display device in which a color filter layer, an overcoat layer, and further partition walls are formed on a thin film transistor (TFT) circuit. It describes that the overcoat layer is made of an organic insulating material such as photoacrylic, and is formed as an insulating layer and a planarizing layer.

[0006] A known method for easily forming the partition wall is to form it by photolithography using a photosensitive composition. Also, a known method for imparting light-shielding properties to the partition wall and suppressing light leakage between pixels is to include a colorant in the photosensitive composition. Patent Document 1 describes a colored photosensitive resin composition that controls the average particle size of the colorant to prevent the occurrence of non-light-emitting regions near the partition walls of light-emitting parts even under conditions of exposure to strong sunlight. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2019-160473 Summary of the Invention [Problem to be solved by the invention]

[0008] Acrylic copolymer resins are generally used as materials for the overcoat layer, but in such cases, thermal decomposition of the main chain or side chain of the acrylic copolymer resin may occur, resulting in outgassing. In an organic electroluminescent device, when a cured product such as a partition wall is formed on the overcoat layer, outgassing from the overcoat layer generated during heat treatment may pass through the partition wall and contaminate the electrodes in the device, or may gradually contaminate the light-emitting layer after the device is formed, which may result in a decrease in light-emitting efficiency or display defects.

[0009] The present inventors have conducted studies and found that the partition walls formed from the colored photosensitive resin composition described in Patent Document 1 do not have sufficient gas barrier properties against outgassing from the overcoat layer.

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition that has excellent gas barrier properties against outgassing from an overcoat layer during heat treatment, and that has excellent development solubility, particularly excellent dissolution time in a developer. Another object of the present invention is to provide a cured product obtained by curing a photosensitive resin composition, a partition wall formed from the cured product, and an organic electroluminescent device and an image display device provided with the partition wall. [Means for solving the problem]

[0011] As a result of extensive investigations, the present inventors have found that the above problems can be solved by using a specific alkali-soluble resin in a photosensitive resin composition, and have thus completed the present invention. That is, the gist of the present invention is as follows.

[0012] [1] A photosensitive resin composition containing (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, The photosensitive resin composition is characterized in that the (b) alkali-soluble resin contains an alkali-soluble resin (b-1) having an isocyanuric ring, a (meth)acryloyloxy group, a carboxy group, and a partial structure represented by the following general formula (4):

[0013] [ka]

[0014] (In formula (4), * represents a bond.) [2] The photosensitive resin composition according to [1], wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (1):

[0015] [ka]

[0016] (In formula (1), R 1 , R 2 , R 3 R each independently represents a hydrogen atom or a monovalent organic group. 1 , R 2 , R 3 At least one of R has a (meth)acryloyloxy group, 1 , R 2 , R 3 At least one of the groups has a partial structure represented by general formula (4), and R 1 , R 2 , R 3 At least one of the groups has a carboxy group. [3] The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (5):

[0017] [ka]

[0018] (In formula (5), Y 1 represents a divalent organic group. * represents a bond. [4] The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (6):

[0019] [ka]

[0020] (In formula (6), Y 2 represents a trivalent organic group. * represents a bond. [5] The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (7):

[0021] [ka]

[0022] (In formula (7), Y 3 represents a tetravalent organic group. * represents a bond. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (2) or the following general formula (3):

[0023] [ka]

[0024] (In formula (2), R 4 ~R 6 R each independently represents an alkylene group, and the alkylene group may be interrupted by an ether oxygen atom. 7 ~R 9 Each independently represents a hydrogen atom or a methyl group. * represents a bond, and at least one of the *'s is bonded to the partial structure represented by general formula (4).

[0025] [ka]

[0026] (In formula (3), R 4 ~R 8 is the same as equation (2). R 10 represents an alkyl group which may have a substituent. * represents a bond, and at least one of the *'s is bonded to the partial structure represented by general formula (4). [7] The photosensitive resin composition according to any one of [1] to [6], further comprising (a) a colorant, wherein the (a) colorant contains an organic color pigment or a black pigment. [8] The photosensitive resin composition according to [7], wherein the content of the colorant (a) is 10 mass % or more based on the total solid content of the photosensitive resin composition. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the content of the alkali-soluble resin (b-1) is 10 mass % or more based on the total mass of the alkali-soluble resin (b).

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the content of the (b) alkali-soluble resin is 100 parts by mass or more per 100 parts by mass of the (d) ethylenically unsaturated compound.

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

[10] , wherein the optical density of the cured coating film per 1 μm of film thickness is 0.5 or more.

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

[11] , which is used for forming partition walls.

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

[11] .

[14]

[13] A partition wall made of hardened material.

[15]

[14] An organic electroluminescent device having a partition wall.

[16]

[14] An image display device having a partition wall. [Effects of the Invention]

[0027] According to the present invention, it is possible to provide a photosensitive resin composition that has excellent gas barrier properties against outgassing from an overcoat layer during heat treatment, and that has excellent development solubility, particularly excellent dissolution time in a developer. [Brief explanation of the drawings]

[0028] [Figure 1] 1-1 to 1-3 in FIG. 1 are schematic top views of substrates for measuring gas barrier properties of the present invention. [Figure 2] 2-1 to 2-3 in FIG. 2 are schematic cross-sectional views of substrates for measuring gas barrier properties of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0029] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist thereof. In the present invention, "(meth)acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth)acrylate" and "(meth)acryloyl". The term "(co)polymer" includes both homopolymers and copolymers, and the terms "acid (anhydride)" and "(anhydrous)...acid" include both acids and their anhydrides.

[0030] In the present invention, the term "acrylic resin" refers to a (co)polymer containing (meth)acrylic acid, or a (co)polymer containing a (meth)acrylic acid ester having a carboxy group. In the present invention, the term "monomer" is the opposite of a so-called high molecular substance (polymer), and includes not only a monomer in the narrow sense but also a dimer, trimer, and oligomer.

[0031] In the present invention, the "total solid content" means the amount of all components other than the solvent contained in the photosensitive resin composition or the pigment dispersion. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solid content. In the present invention, the term "weight average molecular weight" refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography).

[0032] In the present invention, unless otherwise specified, the "amine value" refers to the amine value calculated as the effective solid content, and is a value expressed as the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. The measurement method will be described later. Unless otherwise specified, the "acid value" refers to the acid value calculated as the effective solid content, and is calculated by neutralization titration. With respect to pigments, "CI" means Color Index. In this specification, percentages and parts expressed by "mass" have the same meaning as percentages and parts expressed by "weight".

[0033] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound.

[0034] In the photosensitive resin composition of the present invention, the alkali-soluble resin (b) contains an alkali-soluble resin (b-1) having an isocyanuric ring, a (meth)acryloyloxy group, a carboxy group, and a partial structure represented by formula (4). If necessary, the composition may further contain other ingredients such as (a) a colorant, (e) a solvent, (f) a dispersant, an adhesion improver such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound, and a polymerization inhibitor, and each ingredient is usually used in a dissolved or dispersed state in a solvent.

[0035] <(a) Colorant> The photosensitive resin composition of the present invention may contain (a) a colorant. By containing (a) a colorant, appropriate light absorption properties can be obtained, particularly appropriate light blocking properties when used to form a light blocking member such as a partition wall. The type of colorant (a) that can be used in the photosensitive resin composition of the present invention is not particularly limited, and either a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.

[0036] The pigment contained in the (a) colorant may be one type alone or two or more types. In particular, from the viewpoint of achieving both uniform light blocking in the visible region and OD per unit film thickness, it is preferable to use two or more types. (a) The type of pigment that can be used as the colorant is not particularly limited, but examples thereof include organic color pigments and black pigments. Here, the organic color 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.

[0037] Among pigments, organic pigments are preferred from the viewpoint of high dielectric constant and low dielectric constant. Of these, organic coloring pigments are preferred from the viewpoint of suppressing ultraviolet absorption, high curability, and easy control of the shape of the cured product. Furthermore, black pigments are preferred from the viewpoint of light-blocking properties. The organic color pigment may be used alone or in combination of two or more. In particular, it is more preferable to use a combination of organic color pigments of different colors, and it is even more preferable to use a combination of organic color pigments that exhibit a color close to black.

[0038] The chemical structure of these organic color pigments is not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of pigments that can be used are listed below by pigment number. The "CI" in "CI Pigment Red 2" and other names listed below stands for color index.

[0039] Red pigments include CI 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, 15 1, 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, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 288, 289, 290, 300, 301, 302, 303, 304, 305, 306, 307, 30 5, 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, and 276. In terms of light-blocking properties and dispersibility, preferred are CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254, and more preferred are CI Pigment Red 177, 209, 224, and 254. From the viewpoints of dispersibility and light-shielding properties, it is preferable to use CI Pigment Red 177, 254, or 272. When the photosensitive resin composition is cured with ultraviolet light, it is preferable to use a red pigment with low ultraviolet absorption rate, and from this viewpoint it is more preferable to use CI Pigment Red 254 or 272.

[0040] Examples of orange pigments include CI 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, and 79. From the viewpoints of dispersibility and light-blocking properties, it is preferable to use CI Pigment Orange 13, 43, 64, or 72. When the photosensitive resin composition is cured with ultraviolet light, it is preferable to use an orange pigment with low ultraviolet absorptance, and from this viewpoint, it is more preferable to use CI Pigment Orange 64 or 72.

[0041] Examples of blue pigments include CI 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, and 79. From the viewpoint of light-blocking properties, preferred examples include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60, and more preferred examples include CI Pigment Blue 15:6. From the viewpoints of dispersibility and light-blocking properties, it is preferable to use CI Pigment Blue 15:6, 16, or 60. When the photosensitive resin composition is cured with ultraviolet light, it is preferable to use a blue pigment with low ultraviolet absorption, and from this viewpoint it is more preferable to use CI Pigment Blue 60.

[0042] Examples of purple pigments include CI 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, and 50. From the viewpoint of light-blocking properties, preferred examples include CI Pigment Violet 19, 23, and 29, and more preferred is CI Pigment Violet 23. Note that, from the viewpoints of dispersibility and light-blocking properties, it is preferable to use CI Pigment Violet 23 or 29, and when the photosensitive resin composition is cured with ultraviolet light, it is preferable to use a purple pigment with low ultraviolet absorptance, and from this viewpoint it is more preferable to use CI Pigment Violet 29.

[0043] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and 59. Preferred examples include CI Pigment Green 7 and 36.

[0044] Yellow pigments include CI 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, 1 36, 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, and 208 can be mentioned. Preferred are CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185, and more preferred are CI Pigment Yellow 83, 138, 139, 150, and 180.

[0045] From the viewpoint of the light-blocking properties of the cured product and shape control, it is preferable to use at least one pigment selected from the group consisting of red pigments, orange pigments, blue pigments and purple pigments.

[0046] From the viewpoint of the light-blocking properties of the cured product and shape control, it is preferable to contain at least one of the following pigments. Red pigment: CI Pigment Red 177, 254, 272 Orange pigment: CI Pigment Orange 43, 64, 72 Blue pigment: CI Pigment Blue 15:6, 60 Purple pigment: CI Pigment Violet 23, 29 When two or more organic color pigments are used in combination, the combination of organic color pigments is not particularly limited. However, from the viewpoint of light-blocking properties, it is preferable to contain 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 purple pigments.

[0047] The color combination is not particularly limited, but from the viewpoint of light-blocking properties, examples 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 purple pigment.

[0048] The black pigment may be an organic black pigment or an inorganic black pigment, of which the organic black pigment is preferred from the viewpoint of light-shielding and insulating properties. Among organic black pigments, from the viewpoint of suppressing ultraviolet absorption and making it easier to control the shape, it is preferable to use an organic black pigment containing at least one selected from the group consisting of a compound represented by the following general formula (A1) (hereinafter may be referred to as "compound (A1)"), a geometric isomer of compound (A1), a salt of compound (A1), and a salt of a geometric isomer of compound (A1) (hereinafter may be referred to as "organic black pigment represented by general formula (A1)").

[0049] [ka]

[0050] In formula (A1), R 11 and R 16 each independently represents a hydrogen atom, CH3, CF3, a fluorine atom, or a chlorine atom; R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 are each independently a hydrogen atom, a halogen atom, or R 21 , COOH, COOR 21 , COO - , CONH2, CONHR 21,CONR 21 R 22 , CN, OH, OR 21 , COCR 21 , OOCNH2, OOCNHR 21 , OOCNR 21 R 22 , NO2, NH2, NHR 21 , N.R. 21 R 22 , NHCOR 22 , N.R. 21 COR 22 , N=CH2, N=CHR 21 , N=CR 21 R 22 , S.H., S.R. 21 , SOR 21 , SO2R 21 , SO3R 21 , SO3H, SO3 - , SO2NH2, SO2NHR 21 or SO2NR 21 R 22 represents;R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 may be directly bonded to each other, or may be bonded to an oxygen atom, a sulfur atom, NH, or NR 21 may be connected to each other by a bridge; R 21 and R 22 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.

[0051] Compound (A1) and the geometric isomers of compound (A1) have the following core structure (where the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable.

[0052] [ka]

[0053] When compound (A1) is anionic, it is preferably a salt whose charge is compensated with any known suitable cation, for example, a metal, organic, inorganic, or metal-organic 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. When a geometric isomer of compound (A1) is anionic, it is preferably a similar salt.

[0054] The following substituents in formula (A1) and their definitions tend to have a high shielding rate, and are therefore preferred because they are thought to have no absorption and do not affect the hue of the pigment.

[0055] R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom. R 13 and R 18 are each independently preferably a hydrogen atom, NO2, OCH3, OC2H5, a bromine atom, a chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H or SO3 - is more preferably a hydrogen atom or SO3H, and particularly preferably a hydrogen atom. R 11 and R 16 are each independently preferably a hydrogen atom, CH3 or CF3, more preferably a hydrogen atom.

[0056] Preferably, R 11 and R 16 , R12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 At least one combination selected from the group consisting of 11 is R 16 is identical to R 12 is R 17 is identical to R 13 is R 18 is identical to R 14 is R 19 is identical to and R 15 is R 20 is the same as Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2,2-dimethylpropyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 1,1,3,3-tetramethylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

[0057] Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a thujyl group, a norbornyl group, a bornyl group, a norcaryl group, a caryl group, a menthyl group, a norpinyl group, a pinyl group, an adamantan-1-yl group, and an adamantan-2-yl group.

[0058] Examples of the alkenyl group having 2 to 12 carbon atoms include 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-menthyl-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, and a dodecenyl group.

[0059] Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 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)-thujen-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, and a camphenyl group.

[0060] Examples of the alkynyl group having 2 to 12 carbon atoms include 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-nonyn-9-yl group, a 1-decyn-10-yl group, and a 1-dodecyn-12-yl group.

[0061] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The organic black pigment represented by formula (A1) is preferably an organic black pigment containing at least one compound selected from the group consisting of a compound represented by the following general formula (A2) (hereinafter also referred to as "compound (A2)") and a geometric isomer of compound (A2).

[0062] [ka]

[0063] Such organic black pigments include, for example, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) is an example. This organic black pigment is preferably dispersed using a dispersant, solvent, and method described below before use. Furthermore, if a sulfonic acid derivative of compound (A1), particularly a sulfonic acid derivative of compound (A2), is present during dispersion, dispersibility and storage stability may be improved, so it is preferred that the organic black pigment contains these sulfonic acid derivatives.

[0064] Examples of organic black pigments other than the organic black pigment represented by formula (A1) include aniline black and perylene black. On the other hand, from the viewpoint of higher light-shielding properties, it is preferable to use an inorganic black pigment. Examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black is preferably used from the viewpoint of light-shielding properties and image characteristics. Examples of carbon black include the following carbon blacks.

[0065] 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, #31 50, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

[0066] Manufactured by Degussa: Printex (registered trademark, 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, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

[0067] Cabot Corporation: Monarch (registered trademark, the same applies 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 applies hereinafter) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, the same applies hereinafter) XC72R, ELFTEX (registered trademark)-8

[0068] Biller: RAVEN (registered trademark, the same applies 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 Of these carbon blacks, it is preferable to use acidic carbon black as described in Japanese Patent No. 3644201.

[0069] Carbon black may be coated with a resin. The use of resin-coated carbon black has the effect of improving adhesion to the glass substrate and volume resistivity. Carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used as the resin-coated carbon black. Resin-coated carbon black is preferably used in terms of volume resistivity and dielectric constant.

[0070] The pigment is preferably dispersed and used so that the average particle size is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.25 μm or less, and particularly preferably 0.15 μm or less, where the average particle size is determined by the number of pigment particles. In the photosensitive resin composition of the present invention, the average particle size of the pigment is a value determined from the pigment particle size measured by dynamic light scattering (DLS). The particle size measurement is performed on a sufficiently diluted photosensitive resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2 mass %; however, if a concentration recommended by the measuring instrument is available, that concentration should be followed) at 25°C.

[0071] In addition to organic color pigments and black pigments, dyes may also be used. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0072] Examples of anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60. An example of the phthalocyanine dye is CI Vat Blue 5. Examples of quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9. Examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64. Examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0073] <(b) Alkali-soluble resin> The alkali-soluble resin (b) in the photosensitive resin composition of the present invention contains an alkali-soluble resin (b-1) (hereinafter, sometimes abbreviated as "alkali-soluble resin (b-1)") having an isocyanuric ring, a (meth)acryloyloxy group, a carboxy group, and a partial structure represented by formula (4).

[0074] <Alkali-soluble resin (b-1)> The alkali-soluble resin (b-1) has an isocyanuric ring, a (meth)acryloyloxy group, a carboxy group, and a partial structure represented by formula (4). The alkali-soluble resin (b-1) has an isocyanuric ring, which results in strong intermolecular forces. It is therefore believed that the inclusion of the alkali-soluble resin (b-1) in the photosensitive resin composition blocks the diffusion of outgassing from the overcoat layer in the cured film of the photosensitive resin composition, resulting in good gas barrier properties.

[0075] In addition, since the alkali-soluble resin (b-1) has a (meth)acryloyloxy group and a partial structure represented by formula (4), it is thought that it becomes a stronger cured film when cured with light or heat, and has good gas barrier properties. Furthermore, the alkali-soluble resin (b-1) has a carboxy group, which improves patterning properties. In the alkali-soluble resin (b-1), the isocyanuric ring may be contained in the main chain of the resin skeleton or as a side chain. From the viewpoint of gas barrier properties, it is preferable that the isocyanuric ring be contained in the main chain of the resin skeleton. Furthermore, the alkali-soluble resin (b-1) preferably has a partial structure represented by the following general formula (1).

[0076] [ka]

[0077] In formula (1), R 1 , R 2 , R 3 R each independently represents a hydrogen atom or a monovalent organic group. 1 , R 2 , R 3 At least one of R has a (meth)acryloyloxy group, 1 , R 2 , R 3 At least one of the groups has a partial structure represented by formula (4), and R 1 , R 2 , R 3 At least one of them has a carboxy group.

[0078] (R 1 , R 2 , R 3 ) The monovalent organic group is not particularly limited, but preferred examples include an alkyl group which may have a substituent (which may be interrupted by an etheric oxygen atom in the middle), and an alkenyl group which may have a substituent.

[0079] The alkyl group preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and even more preferably 3 or more carbon atoms. The alkyl group preferably has 14 or less carbon atoms, more preferably 12 or less carbon atoms, and even more preferably 10 or less carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, an isoundecyl group, a dodecyl group, an isododecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, and an isotetradecyl group.

[0080] The alkenyl group preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and even more preferably 3 or more carbon atoms. The number of carbon atoms is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl 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 pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, and a tetradecenyl group.

[0081] Examples of the substituent include a (meth)acryloyloxy group, an alkanoyloxy group, a hydroxyl group, a carboxyl group, and a urethane group. 1 , R 2 , R 3 At least one of the above has a (meth)acryloyloxy group. The hydroxyl group can be reacted with a polybasic acid anhydride to provide a carboxyl group. The carboxyl group can increase the solubility in a developer.

[0082] The connecting site of the carboxy group in the alkali-soluble resin (b-1) is not particularly limited, but the alkali-soluble resin (b-1) preferably has a partial structure represented by the following general formula (5).

[0083] [ka]

[0084] In formula (5), Y 1 represents a divalent organic group. * represents a bond.

[0085] (Y 1 ) Examples of the divalent organic group include alkylene groups having 2 to 4 carbon atoms, alkenylene groups having 2 to 5 carbon atoms, cycloalkylene groups having 4 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, and norbornene groups having 7 to 12 carbon atoms.

[0086] By having the partial structure represented by formula (5), the number of carboxy groups contained in the alkali-soluble resin (b-1) can be increased, thereby increasing the acid value, and the developability of the photosensitive resin composition tends to be improved. Furthermore, by having the partial structure represented by formula (5), the molecular weight of the alkali-soluble resin (b-1) can be increased, the dissolution rate of the photosensitive resin composition during development tends to be slower, and resistance to the developer tends to be improved.

[0087] Examples of the structure having a partial structure represented by formula (5) include those having the following general formula (Y 1 -1)~(Y 1 -10) is an example of a structure. The following general formula (Y 1 -1)~(Y 1 -10) * represents a bond.

[0088] [ka]

[0089] From the viewpoint of ease of synthesis, the structure having the partial structure represented by formula (5) is preferably a structure having the partial structure represented by formula (Y 1 -2), (Y 1 -4), (Y 1 In addition, from the viewpoint of the dissolution rate during development, the structure represented by (Y 1 -7), (Y1 -8), (Y 1 -9), (Y 1 -10) is preferred.

[0090] The connecting site of the carboxy group in the alkali-soluble resin (b-1) is not particularly limited, but the alkali-soluble resin (b-1) preferably has a partial structure represented by the following general formula (6).

[0091] [ka]

[0092] In formula (6), Y 2 represents a trivalent organic group. * represents a bond.

[0093] (Y 2 ) Examples of the trivalent organic group include an optionally substituted benzene ring and an optionally substituted cyclohexane ring.

[0094] By having the partial structure represented by formula (6), the number of carboxy groups contained in the alkali-soluble resin (b-1) can be increased, thereby increasing the acid value, and the developability of the photosensitive resin composition tends to be improved. Furthermore, by having the partial structure represented by formula (6), the molecular weight of the alkali-soluble resin (b-1) can be increased, the dissolution rate of the photosensitive resin composition during development tends to be slower, and resistance to the developer tends to be improved.

[0095] Examples of the structure having a partial structure represented by formula (6) include those having the following general formula (Y 2 -1)~(Y 2 -6), (Y 2 -11)~(Y 2 -16) is an example of a structure represented by the formula: The following general formula (Y 2 -1)~(Y 2 -6), (Y 2 -11)~(Y 2 -16) * represents a bond.

[0096] [ka]

[0097] [ka]

[0098] The connecting site of the carboxy group in the alkali-soluble resin (b-1) is not particularly limited, but the alkali-soluble resin (b-1) preferably has a partial structure represented by the following general formula (7).

[0099] [ka]

[0100] In formula (7), Y 3 represents a tetravalent organic group. * represents a bond.

[0101] (Y 3 ) Examples of the tetravalent organic group include an optionally substituted benzene ring, an optionally substituted benzophenone ring, an optionally substituted biphenyl group, and an optionally substituted fluorenylbisphenol group.

[0102] By having the partial structure represented by formula (7), the number of carboxy groups contained in the alkali-soluble resin (b-1) can be increased, thereby increasing the acid value, and the developability of the photosensitive resin composition tends to be improved. Furthermore, by having the partial structure represented by formula (7), the molecular weight of the alkali-soluble resin (b-1) can be increased, the dissolution rate of the photosensitive resin composition during development tends to be slower, and resistance to the developer tends to be improved.

[0103] Examples of the structure having a partial structure represented by formula (7) include those having the following general formula (Y 3 -1)~(Y 3 -8), (Y3 -11)~(Y 3 -18) is an example of a structure. The following general formula (Y 3 -1)~(Y 3 -8), (Y 3 -11)~(Y 3 -18) * represents a bond.

[0104] [ka]

[0105] [ka]

[0106] The alkali-soluble resin (b-1) preferably has a partial structure represented by the following general formula (2) or a partial structure represented by the following general formula (3) in terms of gas barrier properties and sensitivity.

[0107] [ka]

[0108] In formula (2), R 4 ~R 6 R each independently represents an alkylene group, and the alkylene group may be interrupted by an ether oxygen atom. 7 ~R 9 Each of the *'s independently represents a hydrogen atom or a methyl group. *'s represent bonds, and at least one of the *'s is bonded to the partial structure represented by general formula (4).

[0109] [ka]

[0110] In formula (3), R 4 ~R 8 is the same as equation (2). R 10represents an alkyl group which may have a substituent. * represents a bond, and at least one of the *'s is bonded to the partial structure represented by general formula (4).

[0111] (R 4 , R 5 , R 6 ) In formula (2) and formula (3), R 4 , R 5 , R 6 are each independently an alkylene group which may be interrupted by an etheric oxygen atom. The alkylene group preferably has 1 or more carbon atoms. The alkylene group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 2 or less carbon atoms. For example, the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 2 carbon atoms. The alkylene group may be linear or branched. By keeping the alkylene group at or below the upper limit, developability becomes good and gas barrier properties tend to be improved.

[0112] Examples of alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene groups. These alkylene groups (excluding methylene groups) may be interrupted by an ether oxygen atom. From the viewpoint of gas barrier properties, preferred are methylene, ethylene, and n-propylene groups, and more preferred is methylene.

[0113] (R 10 ) In equation (3), R 10 is an alkyl group which may have a substituent. The alkyl group preferably has 1 or more carbon atoms. The alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms. For example, the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. R 10 The substituent that may be included in the group is not particularly limited, but examples thereof include a hydroxyl group, a methoxy group, an ethoxy group, and a propoxy group.

[0114] R 10From the viewpoint of patterning properties, is preferably an unsubstituted methyl group or an unsubstituted ethyl group, and more preferably an unsubstituted methyl group.

[0115] Specific examples of structures having the partial structure represented by formula (2) include the following structures.

[0116] [ka]

[0117] Specific examples of structures having the partial structure represented by formula (3) include the following structures.

[0118] [ka]

[0119] From the viewpoint of developability and gas barrier properties, the partial structures represented by formula (3-1) and formula (3-2) are more preferred. The alkali-soluble resin (b-1) is a compound represented by the formula (2-1), the formula (5), the formula (4), the formula (Y 1 It is more preferable that the compound has a combination of partial structures represented by the formula (I)-8) from the viewpoints of gas barrier properties, ease of synthesis, and dissolution rate during development.

[0120] <Method for producing alkali-soluble resin (b-1)> When the alkali-soluble resin (b-1) contains an isocyanuric ring in the side chain, the alkali-soluble resin (b-1) may be obtained by copolymerizing a monomer having an isocyanuric ring in the side chain, or by adding an isocyanuric ring to the end of the copolymerized resin.

[0121] When an isocyanuric ring is contained in the main chain of the resin skeleton, the alkali-soluble resin (b-1) can also be produced using an epoxy resin having an isocyanuric ring as a raw material. Examples of epoxy resins having an isocyanuric ring include the following compounds.

[0122] [ka]

[0123] In formula (8), R 4 ~R 6 is equivalent to equation (2).

[0124] Specific examples of the compound represented by formula (8) include the compound represented by the following formula (9).

[0125] [ka]

[0126] In producing the alkali-soluble resin (b-1), an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group can be added to an epoxy resin having an isocyanuric ring. A known method can be used to add an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin having an isocyanuric ring. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin having an isocyanuric ring in the presence of an esterification catalyst at a temperature of 50 to 150°C. Examples of the esterification catalyst that can be used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0127] The epoxy resin having an isocyanuric ring, the α,β-unsaturated monocarboxylic acid, the α,β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may be used singly or in combination of two or more. The amount of isocyanate compound used is preferably in the range of 0.2 to 1.0 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin having an isocyanuric ring, and more preferably in the range of 0.3 to 0.9 equivalents. By setting the amount of isocyanate compound used relative to the epoxy group of the epoxy resin having an isocyanuric ring at or below the lower limit, the molecular weight can be prevented from becoming too small, and curing characteristics tend to be improved. By setting it at or below the upper limit, the molecular weight can be prevented from becoming too large, and solubility in the developer tends to be improved. The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, per equivalent of epoxy group in the epoxy resin having an isocyanuric ring. By using an amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group that is equal to or greater than the lower limit, it is possible to prevent a shortage of unsaturated groups from being introduced, and the subsequent reaction with the polybasic acid and / or its anhydride tends to be more satisfactory. By using an amount equal to or less than the upper limit, it is possible to prevent the remaining unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group, and it is possible to improve curing properties.

[0128] The adduct of the epoxy resin having an isocyanuric ring obtained in the previous step and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group can be subjected to an addition reaction with a polybasic acid and / or an anhydride thereof. Examples of polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Compounds in which the aromatic rings of these polybasic acids or their anhydrides have been partially or completely hydrogenated are also suitable for use.

[0129] Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof, and particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, and trimellitic anhydride.

[0130] The addition reaction of a polybasic acid and / or its anhydride can be carried out using known techniques, and may be continued under conditions similar to those used in the addition reaction of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin having an isocyanuric ring. The amount of polybasic acid and / or its anhydride added is preferably adjusted so that the acid value of the resulting carboxy-containing epoxy (meth)acrylate resin is preferably in the range of 10 to 200 mg KOH / g, more preferably 20 to 180 mg KOH / g. By adjusting the amount to be equal to or greater than the lower limit, alkaline developability tends to be improved, while by adjusting the amount to be equal to or less than the upper limit, curing performance tends to be improved.

[0131] During the addition reaction of the polybasic acid and / or its anhydride, a polyfunctional alcohol (polyhydric alcohol) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, or 1,2,3-propanetriol may be added to introduce a multi-branched structure. The use of a polyhydric alcohol increases the molecular weight of the alkali-soluble resin (b-1), allowing for the introduction of branches into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the introduction rate of acid groups into the molecule can be increased, which tends to facilitate a balance between sensitivity and adhesion.

[0132] An isocyanate compound can be added to an adduct of a polybasic acid and / or its anhydride to an adduct of an epoxy resin having an isocyanuric ring and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group. Examples of the isocyanate compound include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI).

[0133] Preferred are toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), naphthalene diisocyanate (NDI), and hexamethylene diisocyanate (HDI). Particularly preferred are toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).

[0134] The addition reaction of the isocyanate compound can be carried out by a known method, and may be continued under the same conditions as those for the addition reaction of a polybasic acid and / or anhydride thereof to an adduct of an epoxy resin having an isocyanuric ring and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group.

[0135] The weight-average molecular weight (Mw) of the alkali-soluble resin (b-1) is not particularly limited, but is usually 400 or more, preferably 600 or more, more preferably 800 or more, and particularly preferably 1000 or more, and is usually 5000 or less, preferably 4000 or less, more preferably 3000 or less, and particularly preferably 2000. The above upper and lower limits can be arbitrarily combined. For example, 400 to 5000 is preferred, 600 to 4000 is more preferred, 800 to 3000 is even more preferred, and 1000 to 2000 is even more preferred. By setting the Mw at or above the lower limit, excellent gas barrier properties tend to be obtained. By setting the Mw at or below the upper limit, patterning properties tend to be easier to control.

[0136] The acid value of the alkali-soluble resin (b-1) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, even more preferably 40 mgKOH / g or more, even more preferably 50 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 20 to 200 mgKOH / g is preferred, 30 to 150 mgKOH / g is more preferred, 40 to 100 mgKOH / g is more preferred, and 50 to 100 mgKOH / g is even more preferred. By setting the acid value at or above the lower limit, the development solubility is improved and the resolution tends to be good. By setting the acid value at or below the upper limit, the film remaining rate of the photosensitive resin composition tends to be good.

[0137] In the alkali-soluble resin (b-1), the ratio of the total number of moles of carboxy groups to the total number of moles of isocyanuric rings (total number of moles of carboxy groups in the alkali-soluble resin (b-1) / total number of moles of isocyanuric rings in the alkali-soluble resin (b-1)) is preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 0.8 or more. It is also preferably 3.0 or less, more preferably 2.0 or less, even more preferably 1.5 or less, and particularly preferably 1.2 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.2 to 3.0, more preferably 0.2 to 2.0, even more preferably 0.5 to 1.5, and particularly preferably 0.8 to 1.2. Setting it to equal to or greater than the lower limit tends to reduce the hole diameter and improve patterning properties. Setting it to equal to or less than the upper limit tends to improve the curability of the film in a developer.

[0138] In the alkali-soluble resin (b-1), the ratio of the total number of moles of carboxy groups to the total number of moles of the partial structure represented by formula (4) (total number of moles of carboxy groups in the alkali-soluble resin (b-1) / total number of moles of the partial structure represented by formula (4) in the alkali-soluble resin (b-1)) is preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 0.8 or more. It is also preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and particularly preferably 2.5 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.2 to 5.0, more preferably 0.2 to 4.0, even more preferably 0.5 to 3.0, and particularly preferably 0.8 to 2.5. By setting it to be equal to or greater than the lower limit, the hole diameter tends to be smaller and patterning properties tend to be improved. By setting it to be equal to or less than the upper limit, the curability of the film in a developer tends to be improved.

[0139] <Other alkali-soluble resins> The alkali-soluble resin (b) used in the present invention may be a resin other than the alkali-soluble resin (b-1). There are no particular limitations on the resin as long as it contains a carboxyl group or a hydroxyl group, and examples include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing urethane resins, novolac resins, and polyvinylphenol resins. Among these, epoxy (meth)acrylate resins (b-2) and acrylic copolymer resins (b-3) are preferably used from the viewpoint of excellent plate-making properties. These can be used alone or in combination of two or more.

[0140] <Epoxy (meth)acrylate resin (b-2)> The epoxy (meth)acrylate resin (b-2) is a resin obtained by reacting 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 to generate a hydroxyl group, and then reacting the hydroxyl group with a compound having two or more substituents capable of reacting with a hydroxyl group, such as a polybasic acid and / or an anhydride thereof.

[0141] Furthermore, the epoxy (meth)acrylate resin (b-2) also includes a resin obtained by reacting a compound having two or more substituents capable of reacting with a hydroxyl group with the polybasic acid and / or anhydride thereof, followed by the reaction of the polybasic acid and / or anhydride with the hydroxyl group. Furthermore, resins obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group that can further react are also included in the above epoxy (meth)acrylate resin (b-2).

[0142] As described above, epoxy (meth)acrylate resins do not substantially have epoxy groups in their chemical structure, and are not limited to "(meth)acrylates." However, since epoxy compounds (epoxy resins) are used as raw materials and "(meth)acrylates" are a representative example, they are named as such according to convention. As the epoxy (meth)acrylate resin (b-2) used in the present invention, the following epoxy (meth)acrylate resin (b2-1) and / or epoxy (meth)acrylate resin (b2-2) (hereinafter sometimes referred to as "carboxy group-containing epoxy (meth)acrylate resin") are particularly suitable because they have good patterning properties for obtaining small hole diameters, as well as good developability and reliability. Moreover, as the epoxy (meth)acrylate resin (b-2), those having an aromatic ring in the main chain can be more preferably used from the viewpoints of patterning properties and outgassing.

[0143] <Epoxy (meth)acrylate resin (b2-1)> An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, and then reacting it with a polybasic acid and / or its anhydride.

[0144] <Epoxy (meth)acrylate resin (b2-2)> An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, and then reacting the resulting resin with a polyhydric alcohol and a polybasic acid and / or its anhydride. Here, the term "epoxy resin" refers to raw material compounds before they are thermoset to form a resin, and the epoxy resin can be appropriately selected from known epoxy resins. Furthermore, the epoxy resin can be a compound obtained by reacting a phenolic compound with an epihalohydrin. The phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer.

[0145] Suitable types of epoxy resins that can be used as raw materials include, for example, cresol novolac epoxy resins, phenol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, trisphenolmethane epoxy resins, biphenyl novolac epoxy resins, naphthalene novolac epoxy resins, epoxy resins that are reaction products of epihalohydrin with a polyaddition reaction product of dicyclopentadiene and phenol or cresol, adamantyl group-containing epoxy resins, and fluorene epoxy resins. Of these, those having an aromatic ring in the main chain can be more preferably used.

[0146] Examples of epoxy resins include bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark, the same applies hereinafter) 828," "jER1001," "jER1002," and "jER1004")), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (e.g., Nippon Kayaku Co., Ltd.'s "NER-1302" (epoxy equivalent: 323, softening point: 76°C)), and bisphenol F type resins (e.g., "jER807", "EP-4001", "EP-4002", "EP-4004" etc. manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting the alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type Epoxy resins (e.g., "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Corporation, and "DEN-438" manufactured by Dow Chemical Company), (o, m, p-)cresol novolac type epoxy resins (e.g., "EOCN (registered trademark, the same applies hereinafter)-102S," "EOCN-1020," and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), trisphenolmethane type epoxy resins (e.g., "EPPN (registered trademark, the same applies hereinafter)" manufactured by Nippon Kayaku Co., Ltd.), Suitable examples of epoxy resins that can be used include epoxy resins represented by the following general formulas (B1) to (B4): cycloaliphatic epoxy resins (Daicel Corporation's "CELLOXIDE (registered trademark, the same applies hereinafter) 2021P" and "CELLOXIDE EHPE"); epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (for example, DIC Corporation's "EXA-7200" and Nippon Kayaku Co., Ltd.'s "NC-7300"); and epoxy resins represented by the following general formulas (B1) to (B4).Specific examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1); "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2); "E-201" manufactured by Osaka Organic Chemical Industry Ltd. as an epoxy resin represented by the following general formula (B3); and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4).

[0147] [ka]

[0148] In formula (B1), a is an average value and represents a number from 0 to 10, and R 111 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 111 may be the same or different.

[0149] [ka]

[0150] In formula (B2), b1 and b2 each independently represent an average value and a number from 0 to 10; 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 121 may be the same or different.

[0151] [ka]

[0152] In formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), provided that the molecular structure contains one or more adamantane structures.

[0153] [ka]

[0154] In formulas (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group of 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.

[0155] [ka]

[0156] In formula (B4), p and q each independently represent an integer of 0 to 4; 141 and R 142 each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 143 and R 144 each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or greater.

[0157] Among these, it is preferable to use an epoxy resin represented by any one of formulas (B1) to (B4).

[0158] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m-, or p-vinylbenzoic acid, monocarboxylic acids such as (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxyethyl methyl esters. Examples of the monomer include acryloyloxypropyl phthalate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxybutyl succinate, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalate, 2-(meth)acryloyloxybutyl phthalate, 2-(meth)acryloyloxybutyl maleate (meth), a monomer obtained by adding a lactone such as ε-caprolactone, β-propiolactone, γ-butyrolactone or δ-valerolactone to acrylic acid, a monomer obtained by adding an acid (anhydride) such as hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate to succinic acid (anhydride), phthalic acid (anhydride) or maleic acid (anhydride), and a (meth)acrylic acid dimer. In view of sensitivity, (meth)acrylic acid is particularly preferred.

[0159] A known method can be used to add an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150°C. Examples of the esterification catalyst that can be used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0160] The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may each be selected and used alone or in combination of two or more. The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, per equivalent of epoxy group in the epoxy resin. By using an amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group that is equal to or greater than the lower limit, it is possible to prevent a shortage of unsaturated groups from being introduced, and the subsequent reaction with the polybasic acid and / or its anhydride tends to be more satisfactory. On the other hand, by using an amount equal to or less than the upper limit, it is possible to prevent the remaining unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group, and it is likely to improve curing properties.

[0161] Examples of polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

[0162] Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof, and particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

[0163] The addition reaction of a polybasic acid and / or its anhydride can be carried out using known techniques, and the target product can be obtained by continuing the reaction under conditions similar to those of the addition reaction of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin. The amount of polybasic acid and / or its anhydride component added is preferably such that the acid value of the resulting carboxy-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mg KOH / g, more preferably 20 to 140 mg KOH / g. By adjusting the amount to be equal to or greater than the lower limit, alkaline developability tends to be improved, while by adjusting the amount to be equal to or less than the upper limit, curing performance tends to be improved.

[0164] During the addition reaction of the polybasic acid and / or its anhydride, a polyfunctional alcohol (polyhydric alcohol) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, or 1,2,3-propanetriol may be added to introduce a multi-branched structure. In this case, there are no particular restrictions on the order in which the polybasic acid and / or its anhydride and the polyfunctional alcohol are mixed. By heating, the polybasic acid and / or its anhydride undergoes an addition reaction with any hydroxyl group present in the mixture of the reaction product of the epoxy resin with an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group and the polyfunctional alcohol.

[0165] The use of polyhydric alcohols increases the molecular weight of the epoxy (meth)acrylate resin (b-2), allows for the introduction of branches into the molecule, and tends to balance the molecular weight and viscosity. In addition, the introduction rate of acid groups into the molecule can be increased, which tends to make it easier to balance sensitivity, adhesion, etc. In addition to the above-mentioned carboxyl group-containing epoxy (meth)acrylate resins, for example, resins described in Korean Patent Publication No. 10-2013-0022955 can be mentioned.

[0166] The weight-average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin, measured by gel permeation chromatography (GPC) in terms of polystyrene, is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more, and is usually 30,000 or less, preferably 20,000 or less, and more preferably 15,000 or less. The upper and lower limits can be arbitrarily combined. For example, 1,000 to 30,000 is preferred, 1,500 to 20,000 is more preferred, 1,500 to 15,000 is even more preferred, and 2,000 to 15,000 is even more preferred. Setting the Mw to be equal to or greater than the lower limit tends to prevent excessive solubility in the developer. Setting the Mw to be equal to or less than the upper limit tends to facilitate good solubility in the developer.

[0167] The acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. It is also 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 preferred, 60 mgKOH / g to 150 mgKOH / g is more preferred, 80 mgKOH / g to 130 mgKOH / g is even more preferred, and 100 mgKOH / g to 130 mgKOH / g is even more preferred. By setting the acid value at or above the lower limit, the developer solubility is improved, and the resolution tends to be good. By making the content equal to or less than the upper limit, the residual film rate of the photosensitive resin composition tends to be good.

[0168] The chemical structure of the epoxy(meth)acrylate resin is not particularly limited, but from the viewpoint of developability and reliability, it is preferable to contain an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (b2-I) (hereinafter may be abbreviated as "epoxy(meth)acrylate resin (b2-I)") and / or an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (b2-II) (hereinafter may be abbreviated as "epoxy(meth)acrylate resin (b2-II)"):

[0169] [ka]

[0170] In formula (b2-I), R 11 represents a hydrogen atom or a methyl group, and R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (b2-I) may be further substituted with any substituent.

[0171] [ka]

[0172] In formula (b2-II), R 13 each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represents an integer of 0 to 2, and * represents a bond.

[0173] <Epoxy (meth)acrylate resin (b2-I)> The epoxy (meth)acrylate resin having the partial structure represented by formula (b2-I) will be described in detail below.

[0174] [ka]

[0175] In formula (b2-I), R 11 represents a hydrogen atom or a methyl group, and R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (b2-I) may be further substituted with any substituent.

[0176] (R 12 ) In formula (b2-I), R 12 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 in which one or more divalent aliphatic groups are linked with one or more divalent aromatic ring groups. The divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. From the viewpoint of solubility in development, a linear aliphatic group is preferred. On the other hand, from the viewpoint of reducing penetration of a developer into exposed areas, a cyclic aliphatic group is preferred. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits above can be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 1 to 10 is even more preferred. By setting the carbon atom number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon atom number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0177] 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 viewpoint of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which the above-mentioned 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.

[0178] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferred, 1 to 10 is more preferred, and 2 to 10 is even more preferred. By setting the number at or above the lower limit, a strong film tends to be formed and substrate adhesion tends to be good. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0179] Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene ring, or a dicyclopentane ring. From the viewpoint of skeletal rigidity, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred.

[0180] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or 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 preferable that the divalent aliphatic group is unsubstituted. Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 20 is preferred, 5 to 15 is more preferred, and 6 to 10 is even more preferred. By setting the number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0181] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences.

[0182] The aromatic heterocycle in aromatic heterocyclic group can be a single ring or a condensed ring.Examples of aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring, which have two free valences.

[0183] As the divalent aromatic ring group, from the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred. 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. Among these, from the viewpoint of solubility in development, unsubstituted groups are preferred.

[0184] Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved.

[0185] The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved.

[0186] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include groups represented by the following formulae (b2-IA) to (b2-IF): From the viewpoints of skeleton rigidity and film hydrophobicity, the group represented by the following formula (b2-IA) is preferred.

[0187] [ka]

[0188] In formula (b2-I), k represents 1 or 2. From the viewpoint of patterning properties, k is preferably 1, and from the viewpoints of curability, adhesion, and dispersibility during ink production, k is preferably 2. In addition, the epoxy (meth)acrylate resin (b2-I) may contain both a partial structure where k is 1 and a partial structure where k is 2. The benzene ring in formula (b2-I) may be further substituted with any substituent. Examples of the substituent include a hydroxyl 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 properties, it is preferably unsubstituted.

[0189] The partial structure represented by formula (b2-I) is preferably a partial structure represented by the following formula (b2-I-1) from the viewpoint of ease of synthesis.

[0190] [ka]

[0191] In formula (b2-I-1), R 11 , R 12 and k are the same as those in formula (b2-I), and R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond. The benzene ring in formula (b2-I-1) may be further substituted with any substituent. The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or anhydride thereof. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0192] From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid. The benzene ring in formula (b2-I-1) may be further substituted with any substituent. As the substituent, those exemplified for the benzene ring in formula (b2-I) can be preferably used.

[0193] The partial structure represented by formula (b2-I-1) contained in one molecule of the epoxy (meth)acrylate resin (b2-I) may be one type or two or more types, and for example, R X is a hydrogen atom, and R X However, polybasic acid residues may be present in the mixture. The number of partial structures represented by formula (b2-I) contained in one molecule of the epoxy (meth)acrylate resin (b2-I) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, and even more preferably 15 or less. The upper and lower limits above can be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 15 is even more preferred. By setting the number at or above the lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved.

[0194] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (b2-I) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 3000 or more, particularly preferably 4000 or more, and most preferably 5000 or more. It is usually 30000 or less, preferably 20000 or less, and more preferably 15000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1000 to 30000, more preferably 1500 to 2000, even more preferably 1500 to 15000, and even more preferably 2000 to 1500. By setting it to the lower limit or more, the film retention rate of the photosensitive resin composition tends to be good. By setting it to the upper limit or less, the solubility in the developer tends to be good.

[0195] The acid value of the epoxy (meth)acrylate resin (b2-I) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. It is also 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 preferred, 60 mgKOH / g to 150 mgKOH / g is more preferred, 80 mgKOH / g to 130 mgKOH / g is even more preferred, and 100 mgKOH / g to 130 mgKOH / g is even more preferred. By setting the content at or above the lower limit, the development solubility is improved and the resolution tends to be good, whereas by setting the content at or below the upper limit, the residual film rate of the photosensitive resin composition tends to be good.

[0196] Specific examples of the epoxy (meth)acrylate resin (b2-I) are listed below. In the examples, * indicates a bond.

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] <Epoxy (meth)acrylate resin (b2-II)> The epoxy (meth)acrylate resin having the partial structure represented by formula (b2-II) will be described in detail below.

[0202] [ka]

[0203] In formula (b2-II), R 13 each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represents an integer of 0 to 2, and * represents a bond.

[0204] (R 14 ) In formula (b2-II), R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. The cyclic hydrocarbon group may be an aliphatic cyclic group or an aromatic cyclic group. The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, it is easy to suppress deterioration in sensitivity and film loss during development, and resolution tends to be improved.

[0205] The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 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 combined arbitrarily. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is particularly preferred. By setting the carbon number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the carbon number at or below the upper limit, it is easy to suppress deterioration in sensitivity and film loss during development, and resolution tends to be improved.

[0206] Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoints of the residual film rate and resolution of the photosensitive resin composition, an adamantane ring is preferred.

[0207] The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, more preferably 4 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 4 is even more preferred, 2 to 4 is even more preferred, and 3 to 4 is particularly preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved.

[0208] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, 4 to 40 is preferred, 6 to 40 is more preferred, 8 to 30 is more preferred, even more preferably 10 to 20, and particularly preferably 12 to 15. By setting the carbon number at or above the lower limit, a strong film is easily obtained, and surface roughness during development tends to be less likely to occur. By setting the carbon number at or below the upper limit, patterning properties tend to be good.

[0209] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of patterning properties. The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups.

[0210] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred, while cyclic aliphatic groups are preferred from the viewpoint of reducing penetration of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 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, 1 to 25 is preferred, 3 to 20 is more preferred, and 6 to 15 is even more preferred. By setting the carbon number at or above the lower limit, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0211] 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 viewpoint of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group as a side chain.

[0212] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the number at or above the lower limit, a strong film tends to be formed and substrate adhesion tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0213] Examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring, each of which has had two hydrogen atoms removed from it. From the viewpoint of the rigidity of the skeleton, a group in which two hydrogen atoms have been removed from an adamantane ring is preferred. Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or 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 preferable that the divalent aliphatic group is unsubstituted.

[0214] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 30 is preferred, 5 to 20 is more preferred, and 6 to 15 is even more preferred. By setting the number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0215] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences.

[0216] The aromatic heterocycle in aromatic heterocyclic group can be a single ring or a condensed ring.Examples of aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring, which have two free valences.

[0217] As the divalent aromatic ring group, from the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred. Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of solubility in development, it is preferably unsubstituted. Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups.

[0218] The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved.

[0219] The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved.

[0220] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by the above formulae (b2-IA) to (b2-IF). Among these, the group represented by formula (b2-IC) is preferred from the viewpoints of the rigidity of the skeleton and the hydrophobicity of the film. The bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but examples include a mode in which one hydrogen atom of an aliphatic group or aromatic ring group is substituted with the cyclic hydrocarbon group as a side chain, and a mode in which one carbon atom of an aliphatic group is included to form the cyclic hydrocarbon group as a side chain.

[0221] (R 15 , R 16 ) In formula (b2-II), R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent. Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred, while cyclic aliphatic groups are preferred from the viewpoint of reducing penetration of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and 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, 3 to 15 is more preferred, and 6 to 10 is even more preferred. By setting the carbon number at or above the lower limit, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0222] 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 viewpoint of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which the above-mentioned 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.

[0223] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. The upper and lower limits above can be combined arbitrarily. For example, 1 to 12 is preferred, and 2 to 10 is more preferred. By setting the number at or above the lower limit, a strong film tends to be formed and substrate adhesion tends to be good. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be suppressed, and resolution tends to be improved.

[0224] Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, or a dicyclopentadiene ring. From the viewpoint of skeleton rigidity, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring or an adamantane ring are preferred.

[0225] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or 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 preferable that the divalent aliphatic group is unsubstituted.

[0226] (m, n) In formula (b2-II), m and n each independently represent an integer of 0 to 2. By setting the m and n to be equal to or greater than the lower limit, patterning suitability is improved and surface roughness during development tends to be less likely to occur, while by setting the m and n to be equal to or less than the upper limit, developability tends to be improved. From the viewpoint of developability, it is preferable that m and n are 0. On the other hand, from the viewpoint of patterning suitability and surface roughness during development, it is preferable that m and n are 1 or greater.

[0227] The partial structure represented by formula (b2-II) is preferably a partial structure represented by the following general formula (b2-II-1) from the viewpoint of adhesion to a substrate.

[0228] [ka]

[0229] In formula (b2-II-1), R 13 , R 15 , R 16 , m and n are defined as in formula (b2-II), and R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer of 1 or greater, and * represents a bond. The benzene ring in formula (b2-II-1) may be further substituted with any substituent.

[0230] (R α ) In formula (b2-II-1), R α represents an optionally substituted monovalent cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aliphatic cyclic group or an aromatic cyclic group. The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 6 is preferred, 1 to 4 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning properties tend to be good.

[0231] The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 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 combined arbitrarily. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is particularly preferred. By setting the carbon number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the carbon number at or below the upper limit, patterning properties tend to be good.

[0232] Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of strong film properties, an adamantane ring is preferred. The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 2 to 5 is even more preferred, and 3 to 5 is particularly preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning properties tend to be good.

[0233] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, 4 to 30 is preferred, 5 to 20 is more preferred, and 6 to 15 is even more preferred. By setting the number at or above the lower limit, a strong film is more likely to be obtained and surface roughness during development tends to be less likely to occur, while by setting the number at or below the upper limit, patterning properties tend to be good.

[0234] 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 solubility in development, a fluorene ring is preferred. Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxy. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0235] p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 is preferred, and 2 to 3 is more preferred. By making p equal to or greater than the lower limit, the film hardness and film remaining rate tend to be good. By making p equal to or less than the upper limit, the developability tends to be good. From the viewpoint of strong film hardness, R α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

[0236] The benzene ring in formula (b2-II-1) may be further substituted with any substituent. Examples of the substituent include a hydroxyl 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 properties, it is preferably unsubstituted. Specific examples of the partial structure represented by formula (b2-II-1) are listed below.

[0237] [ka]

[0238] [ka]

[0239] [ka]

[0240] [ka]

[0241] [ka]

[0242] The partial structure represented by formula (b2-II) is preferably a partial structure represented by the following general formula (b2-II-2) from the viewpoints of skeleton rigidity and membrane hydrophobicity.

[0243] [ka]

[0244] In formula (b2-II-2), R 13 , R 15 , R 16 , m and n are defined as in formula (b2-II), and R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond. The benzene ring in formula (b2-II-2) may be further substituted with any substituent.

[0245] (R β ) In formula (b2-II-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent. The cyclic hydrocarbon group may be an aliphatic cyclic group or an aromatic cyclic group. The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. The upper and lower limits above can be combined arbitrarily. For example, 1 to 10 is preferred, and 2 to 5 is more preferred. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved.

[0246] The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The upper and lower limits above can be combined arbitrarily. For example, 4 to 40 is preferred, 6 to 35 is more preferred, and 8 to 30 is even more preferred. By setting the carbon number at or above the lower limit, film roughening during development tends to be suppressed. By setting the carbon number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be suppressed, and resolution tends to be improved.

[0247] Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoints of film loss during development and resolution, an adamantane ring is preferred.

[0248] The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 2 to 5 is even more preferred, and 3 to 5 is particularly preferred. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss are easily suppressed, and resolution tends to be improved.

[0249] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, 4 to 40 is preferred, 6 to 30 is more preferred, 8 to 20 is more preferred, and 10 to 15 is particularly preferred. By setting the carbon number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By setting the carbon number at or below the upper limit, it is easy to suppress deterioration in sensitivity and film loss, and resolution tends to be improved.

[0250] 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 developability, a fluorene ring is preferred. Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxy. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0251] From the viewpoint of suppressing film loss and improving resolution, R β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. On the other hand, from the viewpoint of patterning, R β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group. The benzene ring in formula (b2-II-2) may be further substituted with any substituent. Examples of the substituent include a hydroxyl 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. Furthermore, two benzene rings may be linked via a substituent, which may be, for example, a divalent group such as -O-, -S-, -NH-, or -CH2-. From the viewpoint of patterning properties, it is preferably unsubstituted, and from the viewpoint of preventing film loss and the like, it is preferably substituted with a methyl group.

[0252] Specific examples of the partial structure represented by formula (b2-II-2) are shown below. In the examples, * indicates a bond.

[0253] [ka]

[0254] [ka]

[0255] [ka]

[0256] [ka]

[0257] The partial structure represented by formula (b2-II) is preferably a partial structure represented by the following general formula (b2-II-3) from the viewpoints of the coating film remaining rate and patterning properties.

[0258] [ka]

[0259] In formula (b2-II-3), R 13 , R 14 , R 15 , R 16 , m and n are defined as in formula (b2-II), and R Z represents a hydrogen atom or a polybasic acid residue. The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid. In addition, when another OH group is removed, the R Z may be shared with R Z A plurality of formula (b2-II-3) may be linked via the following.

[0260] Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0261] From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid. The partial structure represented by formula (b2-II-3) contained in one molecule of the epoxy (meth)acrylate resin (b2-II) may be one type or two or more types, and for example, R Z is a hydrogen atom, and R Z However, polybasic acid residues may be present in the mixture.

[0262] The number of partial structures represented by formula (b2-II) contained in one molecule of epoxy (meth)acrylate resin (b2-II) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits above can be arbitrarily combined. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 is even more preferred. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss tend to be easily suppressed, and resolution tends to be improved.

[0263] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (b2-II) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and most preferably 5,000 or more. It is usually 10,000 or less, preferably 8,000 or less, and more preferably 7,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 10,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 8,000, even more preferably 2,000 to 8,000, and particularly preferably 2,000 to 7,000. By setting it to the lower limit or higher, the film retention rate of the photosensitive resin composition tends to be good. By setting it to the upper limit or lower, the solubility in the developer tends to be good.

[0264] The acid value of the epoxy (meth)acrylate resin (b2-II) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. It is also 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, it is preferably 20 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, even more preferably 80 mgKOH / g to 130 mgKOH / g, and even more preferably 100 mgKOH / g to 130 mgKOH / g. By setting the acid value at or above the lower limit, the developer solubility is improved, and the resolution tends to be good. By making the content equal to or less than the upper limit, the residual film rate of the photosensitive resin composition tends to be good.

[0265] The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more resins. In addition, a portion of the carboxyl group-containing epoxy (meth)acrylate resin may be replaced with another binder resin. That is, the carboxyl group-containing epoxy (meth)acrylate resin may be used in combination with another binder resin. In this case, the proportion of the carboxyl group-containing epoxy (meth)acrylate resin in the alkali-soluble resin (b) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, and is usually 100% by mass or less.

[0266] As the alkali-soluble resin (b), from the viewpoint of compatibility with pigments, dispersants, etc., it is preferable to use an acrylic copolymer resin (b3), and the resins described in JP 2014-137466 A can be preferably used. Examples of the acrylic copolymer resin (b3) include a copolymer of an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as "unsaturated monomer (b3-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b3-2)").

[0267] Examples of the unsaturated monomer (b3-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids 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 hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid. These unsaturated monomers (b3-1) can be used alone or in combination of two or more.

[0268] Examples of the unsaturated monomer (b3-2) 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;

[0269] 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 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) 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 para-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

[0270] 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, and 3-(vinyloxymethyl)-3-ethyloxetane; Examples include macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane. These unsaturated monomers (b3-2) can be used alone or in combination of two or more.

[0271] In the copolymer of the unsaturated monomer (b3-1) and the unsaturated monomer (b3-2), the copolymerization ratio of the unsaturated monomer (b3-1) is preferably 5 to 50 mass %, more preferably 10 to 40 mass %. By copolymerizing the unsaturated monomer (b3-1) in such a range, a photosensitive resin composition excellent in alkali developability and storage stability tends to be obtained.

[0272] Examples of the copolymer of the unsaturated monomer (b3-1) and the unsaturated monomer (b3-2) include the copolymers disclosed in Japanese Patent Application Laid-Open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728.

[0273] The copolymer of the unsaturated monomer (b3-1) and the unsaturated monomer (b3-2) can be produced by known methods. For example, the structure, Mw, and Mw / Mn can be controlled by the methods disclosed in JP 2003-222717 A, JP 2006-259680 A, and WO 2007 / 029871 A. In addition, resins described in WO 2016 / 194619 and WO 2017 / 154439 may also be used.

[0274] <(c) Photopolymerization initiator> (c) Photopolymerization initiator is a component that directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and generates polymerization-active radicals. If necessary, additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added. Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in JP-A-10-39503; α-aminoalkylphenone derivatives; and oxime ester compounds described in JP-A-2000-80068 and JP-A-2006-36750.

[0275] Examples of the metallocene compound include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl), dicyclopentadienyltitanium di(2,6-difluorophenyl), dicyclopentadienyltitanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), and dicyclopentadienyltitanium[2,6-difluoro-3-(pyrro-1-yl)phenyl].

[0276] 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.

[0277] 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.

[0278] 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.

[0279] 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, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0280] As a photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate-making properties, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, for example, an oxime ester compound with such excellent sensitivity is particularly useful. Because an oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, it has high sensitivity even in a small amount and is stable against thermal reactions, making it possible to obtain a highly sensitive photosensitive resin composition with a small amount.

[0281] Examples of the oxime ester compounds include compounds represented by the following general formula (IV).

[0282] [ka]

[0283] In formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 21b represents an optional substituent containing an aromatic ring. R 22arepresents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent. n represents an integer of 0 or 1.

[0284] R 21a In the formula (I), the number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in a developer and sensitivity, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group.

[0285] Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl 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 preferable that the alkyl group is unsubstituted. R 21a Examples of the aromatic ring group in include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Furthermore, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less.

[0286] 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 preferred, and a phenyl group is more preferred. 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 in which these substituents are linked together. From the viewpoint of developability, an alkyl group, an alkoxy group, or a group in which these substituents are linked together is preferred, and a linked alkoxy group is more preferred. R 21bExamples of the group include an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted diphenyl sulfide group. Among these, 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.

[0287] R 22a In the formula, the number of carbon atoms in the alkanoyl group is not particularly limited, but from the viewpoint of solubility in a developer and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. Examples thereof 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 carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, it is preferable that the alkanoyl group is unsubstituted.

[0288] R 22a The number of carbon atoms in the aryloyl group is not particularly limited, but from the viewpoint of solubility in a developer and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Examples include a benzoyl group and a naphthoyl group. Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferable that the aryloyl group is unsubstituted.

[0289] From a sensitivity perspective, R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

[0290] The initiators described in JP 2016-133574 A are also preferably used because they reduce contamination of the liquid crystal layer by colorants.

[0291] The photopolymerization initiator may be used alone or in combination of two or more. The photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocycle 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, pyrromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, and JP-A-54-155293. Examples of dyes having a dialkylaminobenzene skeleton include those described in JP-B No. 45-37377, JP-A No. 48-84183, JP-A No. 52-112681, JP-A No. 58-15503, JP-A No. 60-88005, JP-A No. 59-56403, JP-A No. 2-69, JP-A No. 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, and JP-A No. 4-288818.

[0292] The sensitizing dye is preferably an amino group-containing sensitizing dye, and more preferably a compound having an amino group and a phenyl group in the same molecule. Examples thereof include benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 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, and 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole.

[0043] A p-dialkylaminophenyl group-containing compound such as 4,4'-dialkylaminophenyl)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, or (p-diethylaminophenyl)pyrimidine is preferred, and 4,4'-dialkylaminobenzophenone is particularly preferred. The sensitizing dyes may be used alone or in combination of two or more.

[0293] Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described below. One type of polymerization accelerator may be used alone, or two or more types may be used in combination.

[0294] <(d) Ethylenically unsaturated compounds> The photosensitive resin composition of the present invention contains (d) an ethylenically unsaturated compound. By containing (d) an ethylenically unsaturated compound, sensitivity is improved. The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule, such as (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and monoester of polyhydric or monohydric alcohol.

[0295] In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is usually two or more, preferably four or more, more preferably five or more, and preferably eight or less, more preferably seven or less. The above upper and lower limits can be combined arbitrarily. For example, 2 to 8 groups are preferred, 2 to 7 are more preferred, 4 to 7 are even more preferred, and 5 to 7 are particularly preferred. By setting the number at or above the lower limit, high sensitivity tends to be achieved. By setting the number at or below the upper limit, solubility in a developer tends to be improved.

[0296] Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

[0297] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylates 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, and glycerol acrylate; methacrylic acid esters in which the acrylate is replaced with methacrylate; itaconic acid esters in which itaconate is replaced with itaconate; crotonate esters in which crotonate is replaced with crotonate; and maleic acid esters in which maleate is replaced with maleate.

[0298] 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, and pyrogallol triacrylate. The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single compound, but examples thereof include a condensate of acrylic acid, phthalic acid, and ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensate of acrylic acid, adipic acid, butanediol, and glycerin.

[0299] Other examples of the polyfunctional ethylenic monomer used in the present invention include urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as the addition reaction product of a polyfunctional epoxy compound with a hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

[0300] Examples of urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), and UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).

[0301] From the viewpoint of curability, it is preferable to use a (meth)acrylic acid alkyl ester as the (d) ethylenically unsaturated compound, and it is more preferable to use dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.

[0302] <(e) Solvent> The photosensitive resin composition of the present invention may contain (e) a solvent. By containing (e) a solvent, each component of the photosensitive resin composition can be dispersed or dissolved in the solvent, and coating becomes easy. The photosensitive resin composition of the present invention is usually used in a state in which (b) alkali-soluble resin, (c) photopolymerization initiator, (d) ethylenically unsaturated compound, and optionally used (a) colorant, (f) dispersant, and various other materials are dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoints of dispersibility and coatability.

[0303] Among organic solvents, from the viewpoint of coatability, it is preferable to select one having a boiling point of 100 to 300° C., more preferably 120 to 280° C. Note that the boiling point here means the boiling point at a pressure of 1013.25 hPa, and the same applies to all boiling points hereinafter. Examples of such organic solvents include 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;

[0304] 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; 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, and 3-methyl-3-methoxybutyl acetate;

[0305] glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol 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, and dihexyl ether;

[0306] 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, and methoxymethyl pentanone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol;

[0307] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0308] 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, and γ-butyrolactone;

[0309] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile;

[0310] Examples of commercially available organic solvents include mineral spirits, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal 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 applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all of which are trade names). These organic solvents may be used alone or in combination of two or more kinds.

[0311] When the partition walls are formed by photolithography, the organic solvent to be selected preferably has a boiling point of 100 to 240°C, more preferably 120 to 200°C, and even more preferably 120 to 170°C. Glycol alkyl ether acetates are preferred because they have a good balance of application properties, surface tension, etc., and the solubility of the components in the composition is relatively high.

[0312] Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as organic solvents to be used in combination. Among these, propylene glycol monomethyl ether is particularly preferred due to its ability to dissolve the components in the composition. Glycol monoalkyl ethers have high polarity, and adding too much tends to cause the pigment to aggregate, resulting in a decrease in storage stability, such as an increase in the viscosity of the resulting photosensitive resin composition. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

[0313] It is also preferable to use an organic solvent with a boiling point of 150°C or higher (hereinafter sometimes referred to as a "high-boiling solvent"). The use of such a high-boiling solvent makes the photosensitive resin composition more difficult to dry, but it also has the effect of preventing the uniform dispersion of the pigment in the composition from being destroyed by rapid drying. In other words, it has the effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of colorants, for example, at the tip of a slit nozzle. Because of these high effects, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred among the various solvents mentioned above.

[0314] When a high-boiling solvent is used in combination, the content of the high-boiling solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting the content at or above the lower limit, it tends to be possible to prevent, for example, the coloring material or the like from precipitating and solidifying at the tip of the slit nozzle, which could cause foreign matter defects, while by setting the content at or below the upper limit, it tends to be possible to prevent the drying temperature of the composition from becoming slow, which tends to prevent problems such as poor tact time in the reduced-pressure drying process and pin marks during pre-baking. The high-boiling solvent having a boiling point of 150°C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to separately add a high-boiling solvent having a boiling point of 150°C or higher.

[0315] Preferred high-boiling point 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-hexanol diacetate, and triacetin.

[0316] <(f) Dispersant> When the photosensitive resin composition of the present invention contains (a) a colorant, it is important to finely disperse (a) the colorant and stabilize the dispersed state in order to ensure stable quality, and therefore it is preferable that the photosensitive resin composition contain (f) a dispersant. As the (f) dispersant, a polymer dispersant having a functional group is preferred, and furthermore, from the viewpoint of dispersion stability, a polymer dispersant having a functional group such as a carboxyl group, a phosphate group, a sulfonic acid group, or a base thereof, a primary, secondary, or tertiary amino group, a quaternary ammonium base, or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferred. Among these, a polymer dispersant having a basic functional group such as a primary, secondary, or tertiary amino group, a quaternary ammonium base, or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is particularly preferred from the viewpoint that the pigment can be dispersed with a small amount of dispersant.

[0317] 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. The polymer dispersant may be used alone or in combination of two or more kinds.

[0318] Examples of dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemicals), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Inc.).

[0319] The weight-average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1,000 or more, and preferably 100,000 or less, more preferably 50,000 or less. The above upper and lower limits can be combined arbitrarily. For example, the weight-average molecular weight (Mw) of the polymer dispersant is preferably 700 to 100,000, more preferably 1,000 to 50,000.

[0320] Examples of urethane-based and acrylic-based dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic-based) (all manufactured by BYK-Chemie). From the viewpoints 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.

[0321] (f) The dispersant preferably includes an acrylic dispersant. Acrylic dispersants have a flexible main skeleton with a linear molecular structure, and it is believed that many of the adsorbing groups adsorb to the colorant, thereby uniformly dispersing the colorant in the photosensitive resin composition and pigment dispersion. Uniform distribution of the colorant in the coating film results in a dense coating film. Furthermore, uniform distribution of the colorant, which is a component insoluble in alkaline developer, in the coating film suppresses penetration of the developer into the coating film during development, improving pattern adhesion, particularly for fine patterns. It is believed that this improves adhesion. The acrylic dispersant preferably contains a nitrogen atom.

[0322] As the acrylic dispersant, it is preferable to use a random copolymer, graft copolymer, or block copolymer of an unsaturated group-containing monomer having a functional group (the functional group here refers to the functional group contained in the polymer dispersant described above) and an unsaturated group-containing monomer not having a functional group. These copolymers can be produced by known methods. Examples of the unsaturated group-containing monomer having a functional group include unsaturated monomers having a carboxy group, such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and acrylic acid dimer; and unsaturated monomers having a tertiary amino group or a quaternary ammonium salt group, such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternized products thereof. These may be used alone or in combination of two or more.

[0323] Examples of unsaturated group-containing monomers that do not have a functional group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecane (meth), ) acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide, acrylonitrile, vinyl acetate, and macromonomers such as polymethyl (meth)acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth)acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. These may be used alone or in combination of two or more.

[0324] From the viewpoint of dispersibility, the acrylic dispersant is preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. In this case, in addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the A block may also contain a partial structure derived from the unsaturated group-containing monomer not containing the functional group, and these may be contained in the A block in the form of either random copolymerization or block copolymerization. The content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, and particularly preferably 0% by mass.

[0325] From the viewpoint of dispersibility, the B block is preferably composed only of a partial structure derived from an unsaturated group-containing monomer that does not contain the above-mentioned functional group, and one B block may contain partial structures derived from two or more types of monomers, and these may be contained in the B block in either a random copolymerization or block copolymerization mode.

[0326] The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below. Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods. Of these, anionic living polymerization methods use anions as the active species for polymerization, and are represented, for example, by the following scheme.

[0327] [ka]

[0328] In the above scheme, Ar 1 is a monovalent organic group, and Ar 2 Ar 1 M is a metal atom, and s and t are each an integer of 1 or more. In the radical living polymerization method, the active species for polymerization are radicals, and for example, the method is shown in the following scheme.

[0329] [ka]

[0330] In the above scheme, Ar 1 is a monovalent organic group, and Ar 2 Ar 1 j and k are each an integer of 1 or more, and R a is a hydrogen atom or a monovalent organic group, and R b is R a is a hydrogen atom or a monovalent organic group different from When synthesizing acrylic dispersants, for example, the following methods are known: Japanese Patent Application Laid-Open No. 9-62002; P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984); BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute et al., Polym. J. 17, 977 (1985); K. Hatada, K. Ute et al. al, Polym. J. 18, 1037 (1986); Koichi Migite, Koichi Hatada, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Research Papers, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985); DY Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473 (1987) can be used.

[0331] The acrylic dispersant usable in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block / B block ratio constituting the copolymer is not particularly limited, but is preferably 1 / 99 to 80 / 20 (mass ratio), and more preferably 5 / 95 to 60 / 40 (mass ratio). By keeping the ratio within this range, it tends to be easier to ensure a balance between dispersibility and storage stability.

[0332] The amount of quaternary ammonium salt group per gram of the AB block copolymer or BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By keeping it within this range, good dispersibility tends to be easily ensured. The acrylic dispersant may contain an amino group. The amine value of the acrylic dispersant is usually 1 to 130 mgKOH / g. It is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, even more preferably 50 mgKOH / g or more, and particularly preferably 60 mgKOH / g or more. It is also preferably 120 mgKOH / g or less, 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, it is preferably 10 to 120 mgKOH / g, more preferably 30 to 100 mgKOH / g, even more preferably 50 to 90 mgKOH / g, and particularly preferably 60 to 80 mgKOH / g. Setting it to be equal to or greater than the lower limit tends to improve dispersibility, while setting it to be equal to or less than the upper limit tends to improve storage stability after dispersion.

[0333] The amine value of an acrylic dispersant is expressed as the mass of KOH equivalent to the amount of base per gram of solids excluding the solvent in a dispersant sample, and is measured by the following method. Accurately weigh out 0.5-1.5 g of dispersant sample into a 100 mL beaker and dissolve in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, neutralize this solution with a 0.1 mol / L HClO4 acetic acid solution. The inflection point on the titration pH curve is used as the titration endpoint, and the amine value is calculated using the following formula.

[0334] Amine value [mgKOH / g] = (561 × V) / (W × S) (where W is the weight of the dispersant sample [g], V is the titration amount at the end of the titration [mL], and S is the solids concentration of the dispersant sample [% by mass]). The weight-average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more, and is preferably 50,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1,000 to 50,000 is preferred, 3,000 to 50,000 is more preferred, 4,000 to 20,000 is more preferred, and 5,000 to 15,000 is particularly preferred. Setting the Mw at or above the lower limit tends to improve dispersibility, while setting the Mw at or below the upper limit tends to reduce viscosity changes.

[0335] When the acrylic dispersant has a quaternary ammonium salt group as a functional group, the chemical structure of the repeating unit containing the quaternary ammonium salt group is not particularly limited. However, from the viewpoint of dispersibility, it is preferable that the acrylic dispersant has a repeating unit represented by the following general formula (V) (hereinafter, sometimes referred to as "repeating unit (V)"):

[0336] [ka]

[0337] In formula (V), R 31 ~R 33 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and R 31 ~R 33 Two or more of R may be bonded to each other to form a cyclic structure. 34 is a hydrogen atom or a methyl group; X is a divalent linking group; Y - is the counteranion. R in formula (V) 31 ~R 33The number of carbon atoms in the alkyl group, which may have a substituent, is not particularly limited, but is usually 1 or more, preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 2 or less. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, with methyl, ethyl, propyl, butyl, pentyl, and hexyl groups being preferred, methyl, ethyl, propyl, and butyl being more preferred, and methyl and ethyl being even more preferred. The alkyl group may be either linear or branched. It may also be one having a cyclic structure, such as a cyclohexyl group or a cyclohexylmethyl group.

[0338] R in formula (V) 31 ~R 33 The number of carbon atoms in the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, and preferably 16 or less, and more preferably 12 or less. Examples include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group, with a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group being preferred, and a phenyl group, a methylphenyl group, and an ethylphenyl group being more preferred.

[0339] R in formula (V) 31 ~R 33 The number of carbon atoms in the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, and preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. Examples include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, with a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylbutylene group being preferred, and a phenylmethylene group and a phenylethylene group being more preferred.

[0340] From the perspective of variance, R 31 ~R 33are each independently an alkyl group or an aralkyl group, and specifically, R 31 and R 33 are each independently a methyl group or an ethyl group, and R 32 is preferably a phenylmethylene group or a phenylethylene group, and R 31 and R 33 is a methyl group, and R 32 is more preferably a phenylmethylene group.

[0341] When the polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following general formula (VI) (hereinafter sometimes referred to as "repeating unit (VI)") from the viewpoint of dispersibility.

[0342] [ka]

[0343] In formula (VI), R 35 and R 36 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and R 35 and R 36 may be bonded to each other to form a ring structure. 37 is a hydrogen atom or a methyl group. Z is a divalent linking group.

[0344] R in formula (VI) 35 and R 36 In the formula (V), the alkyl group which may have a substituent is R 31 ~R 33 The examples given below can be preferably used. R in formula (VI) 35 and R 36 In the formula (V), the aryl group which may have a substituent is R 31 ~R 33 The examples given below can be preferably used. R in formula (VI)35 and R 36 In the formula (V), the aralkyl group which may have a substituent is R 31 ~R 33 The examples given below can be preferably used. From the perspective of variance, R 35 and R 36 are each independently preferably an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group.

[0345] R in formula (V) 31 ~R 33 and R of formula (VI) 35 and R 36 Examples of the substituent that the alkyl group, aralkyl group or aryl group in the formula (I) may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

[0346] In formula (V) and formula (VI), examples of the divalent linking groups X and Z include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 -GROUP, -COOR 44 - group [wherein R 43 and R 44 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, and preferably —COO—R 44 - group, more preferably a -COO-C2H4- group. In formula (V), the counter anion Y - Examples include Cl - , Br - , I - , ClO4 - , BF4 - , CH3COO - , PF6 - , CH3SO4 - Examples include:

[0347] The content of the repeating unit represented by formula (V) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 35 mol% or less, and also preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and particularly preferably 30 mol% or more, based on the total content of the repeating unit represented by formula (V) and the repeating unit represented by formula (VI). The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, even more preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol%.

[0348] The proportion of the repeating unit represented by formula (V) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, even more preferably 5 to 20 mol%, and particularly preferably 10 to 15 mol%.

[0349] The content of the repeating unit represented by formula (VI) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 100 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, particularly preferably 70 mol% or less, and also preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, and particularly preferably 60 mol% or more, based on the total content of the repeating unit represented by formula (V) and the repeating unit represented by formula (VI). The above upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 100 mol%, more preferably 30 to 90 mol%, even more preferably 50 to 80 mol%, and particularly preferably 60 to 70 mol%.

[0350] The proportion of the repeating unit represented by formula (VI) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, particularly preferably 25 mol% or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 60 mol% or less, more preferably 10 to 40 mol% or less, even more preferably 15 to 30 mol% or less, particularly preferably 20 to 25 mol% or less.

[0351] From the viewpoint of increasing compatibility with binder components such as solvents and improving dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following general formula (VII) (hereinafter sometimes referred to as "repeating unit (VII)").

[0352] [ka]

[0353] In formula (VII), R 40 is an ethylene group or a propylene group, and R 41is an alkyl group which may have a substituent, and R 42 is a hydrogen atom or a methyl group, and n is an integer of 1 to 20. R in formula (VII) 41 The number of carbon atoms in the alkyl group, which may have a substituent, is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, with methyl, ethyl, propyl, butyl, pentyl, and hexyl groups being preferred, and methyl, ethyl, propyl, and butyl being more preferred. The alkyl group may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0354] In terms of compatibility and dispersibility in binder components such as solvents, n in formula (VII) is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less. The upper and lower limits can be arbitrarily combined. For example, n is preferably 1 to 10, more preferably 2 to 5.

[0355] The content of the repeating unit represented by formula (VII) in all repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 4 to 10 mol% is even more preferred. Within the above ranges, compatibility with binder components such as solvents and dispersion stability tend to be compatible.

[0356] From the viewpoint of increasing the compatibility of the dispersant with binder components such as solvents and improving dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following general formula (VIII) (hereinafter sometimes referred to as "repeating unit (VIII)"):

[0357] [ka]

[0358] In formula (VIII), R 38 R is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. 39 is a hydrogen atom or a methyl group.

[0359] R in formula (VIII) 38 The number of carbon atoms in the alkyl group, which may have a substituent, is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl groups, with methyl, ethyl, propyl, butyl, pentyl, hexyl, and 2-ethylhexyl groups being preferred, and methyl, ethyl, propyl, butyl, and 2-ethylhexyl being more preferred. The alkyl group may be either linear or branched. It may also contain a cyclic structure, such as a cyclohexyl group or a cyclohexylmethyl group.

[0360] R in formula (VIII) 38The number of carbon atoms in the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. Examples include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group, with a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group being preferred, and a phenyl group, a methylphenyl group, and an ethylphenyl group being more preferred.

[0361] R in formula (VIII) 38 The number of carbon atoms in the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. Examples include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, with a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylbutylene group being preferred, and a phenylmethylene group and a phenylethylene group being more preferred.

[0362] From the viewpoint of solvent compatibility and dispersion stability, R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group or a phenylmethylene group.

[0363] R 38 In the formula (I), examples of the substituent that the alkyl group may have include a halogen atom and an alkoxy group. Also, examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. R 38 The chain alkyl group represented by the formula (I) includes both straight chain and branched chain alkyl groups.

[0364] From the viewpoint of dispersibility, the content of the repeating unit represented by formula (VIII) in all repeating units of the dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and is preferably 80 mol% or less, more preferably 70 mol% or less. The above upper and lower limits can be arbitrarily combined. For example, 30 to 80 mol% is preferred, 40 to 80 mol% is more preferred, and 50 to 70 mol% is even more preferred.

[0365] The acrylic dispersant may have a repeating unit other than the repeating unit (V), the repeating unit (VI), the repeating unit (VII), and the repeating unit (VIII). Examples of such a repeating unit include repeating units derived from a styrene-based monomer such as styrene or α-methylstyrene; a (meth)acrylate-based monomer such as (meth)acrylic acid chloride; a (meth)acrylamide-based monomer such as (meth)acrylamide or N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonate glycidyl ether; and N-methacryloylmorpholine.

[0366] From the viewpoint of further improving dispersibility, the acrylic dispersant is preferably a block copolymer having an A block containing repeating units (V) and (VI) and a B block not containing repeating units (V) and (VI), and is preferably an AB block copolymer or a BAB block copolymer. Introducing a tertiary amino group as well as a quaternary ammonium salt group into the A block tends to significantly improve the dispersing ability of the dispersant. Furthermore, the B block preferably contains repeating units (VII), and more preferably further contains repeating units (VIII).

[0367] In the A block, the repeating unit (V) and the repeating unit (VI) may be contained in either a random copolymerization or a block copolymerization manner. Furthermore, two or more types of each of the repeating unit (V) and the repeating unit (VI) may be contained in one A block, and in this case, each repeating unit may be contained in the A block in either a random copolymerization or a block copolymerization manner.

[0368] The A block may contain repeating units other than the repeating units (V) and (VI), and examples of such repeating units include the repeating units derived from the (meth)acrylic acid ester monomers described above. The content of repeating units other than the repeating units (V) and (VI) in the A block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, and it is particularly preferred that such repeating units are not contained in the A block.

[0369] The B block may contain repeating units other than repeating units (VII) and (VIII), and examples of such repeating units include repeating units derived from monomers such as styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonate glycidyl ether; and N-methacryloylmorpholine. The content of repeating units other than repeating units (VII) and (VIII) in the B block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, and it is particularly preferred that such repeating units are not contained in the B block.

[0370] These acrylic dispersants may be used alone or in combination of two or more. In terms of improving dispersion stability, it is preferable to use the dispersant (f) in combination with a pigment derivative, which will be described later.

[0371] <Other ingredients of the photosensitive resin composition> In addition to the above-mentioned components, the photosensitive resin composition of the present invention may appropriately contain additives such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors.

[0372] (1) Adhesion improver The photosensitive resin composition of the present invention may contain an adhesion promoter to improve adhesion to the substrate. Preferred examples of the adhesion promoter include silane coupling agents and phosphoric acid group-containing compounds. As the type of silane coupling agent, various types such as epoxy-based, (meth)acrylic-based, and amino-based agents can be used alone or in combination of two or more.

[0373] Examples of silane coupling agents include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, and isocyanatesilanes such as 3-isocyanatepropyltriethoxysilane. Epoxysilane silane coupling agents are particularly preferred.

[0374] As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphates are preferred, and those represented by the following general formula (g1), (g2) or (g3) are preferred.

[0375] [ka]

[0376] In formulas (g1), (g2) and (g3), R 51represents a hydrogen atom or a methyl group; l and l' are integers of 1 to 10; and m is 1, 2, or 3. These phosphate group-containing compounds may be used alone or in combination of two or more.

[0377] (2) Surfactants The photosensitive resin composition of the present invention may contain a surfactant to improve coating properties. As the surfactant, various surfactants can be used, for example, anionic, cationic, nonionic, amphoteric surfactants, etc. Among them, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and fluorine-based and silicon-based surfactants are particularly effective in terms of coatability. Examples of 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 Silicones), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar Co., Ltd.), and FC4430 (manufactured by 3M). The surfactant may be used alone or in any combination of two or more in any ratio.

[0378] (3) Pigment derivatives The photosensitive resin composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.

[0379] Examples of pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives, with phthalocyanine-based and quinophthalone-based derivatives being preferred. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and its quaternary salts, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc., which are bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., and preferably a sulfonic acid group. A single pigment skeleton may contain multiple such substituents.

[0380] Examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.

[0381] (4) Mercapto compounds A mercapto compound may be added as a polymerization accelerator or to improve adhesion to the substrate. Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis( mercapto compounds having a heterocycle, such as 1,3,5-tris(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), and 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 singly or in combination of two or more.

[0382] (5) Polymerization inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. The inclusion of a polymerization inhibitor inhibits radical polymerization of the lower layer of the coating film, which is thought to enable control of the taper angle (the angle between the support and the cured product in the cross section of the cured product).

[0383] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, 2,6-di-tert-butyl-4-cresol is preferred from the viewpoint of shape control. Furthermore, hydroquinone monomethyl ether and methylhydroquinone are preferred from the viewpoint of safety for the human body. The polymerization inhibitors can be used alone or in combination of two or more.

[0384] (b) When an alkali-soluble resin is produced, a polymerization inhibitor may be contained in the resin, and this may be used as the polymerization inhibitor of the present invention. Alternatively, in addition to the polymerization inhibitor contained in the resin, a polymerization inhibitor identical to or different from the polymerization inhibitor may be added during the production of the photosensitive resin composition. When the photosensitive resin composition contains a polymerization inhibitor, its content is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, based on the total solid content of the photosensitive resin composition. The upper and lower limits can be arbitrarily combined. For example, 0.0005% by mass to 0.3% by mass is preferred, 0.001% by mass to 0.2% by mass is more preferred, and 0.01% by mass to 0.1% by mass is even more preferred. By setting the content at or above the lower limit, the shape of the cured product tends to be more controllable. By setting the content at or below the upper limit, the required sensitivity tends to be maintained.

[0385] <Contents of each component in the photosensitive resin composition> When the photosensitive resin composition contains (a) a colorant, the content of the (a) colorant is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% 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, 5 to 50% by mass is preferred, more preferably 10 to 40% by mass, even more preferably 15 to 40% by mass, even more preferably 15 to 30% by mass, and particularly preferably 15 to 25% by mass. By setting the content at or above the lower limit, light-blocking properties tend to be ensured. By setting the content at or below the upper limit, the amount of dispersant can be reduced, which tends to suppress surface roughness.

[0386] When the photosensitive resin composition contains an organic coloring pigment, its content is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more, based on the total solid content of the photosensitive resin composition. It is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 70% by mass, more preferably 10 to 70% by mass, even more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass. By setting the content at or above the lower limit, light-blocking properties tend to be enhanced. By setting the content at or below the upper limit, the amount of dispersant can be reduced, which tends to suppress surface roughness.

[0387] When the (a) colorant contains a red pigment and / or an orange pigment, the total content of the red pigment and the orange pigment is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, particularly preferably 12% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total mass of the (a) colorant. The above upper and lower limits can be arbitrarily combined. For example, 5 to 40% by mass is preferred, 8 to 40% by mass is more preferred, 10 to 30% by mass is more preferred, and 12 to 20% by mass is particularly preferred. Setting the content at or above the lower limit tends to result in a color tone close to black. Setting the content at or below the upper limit tends to result in high sensitivity.

[0388] When the (a) colorant contains a blue pigment and / or a violet pigment, the total content of the blue pigment and the violet pigment is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, relative to the total mass of the (a) colorant. It is also preferably 95% by mass or less, more preferably 92% by mass or less, and particularly preferably 90% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, even more preferably 70 to 92% by mass, and particularly preferably 80 to 90% by mass. Setting it to be equal to or greater than the lower limit tends to produce a color tone close to black. Setting it to be equal to or less than the upper limit tends to improve sensitivity and light-blocking properties.

[0389] When the (a) colorant contains both a red pigment and / or an orange pigment and a blue pigment and / or a violet pigment, the content of the red pigment and / or the orange pigment relative to 100 parts by mass of the blue pigment and / or the violet pigment is not particularly limited, but is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, particularly preferably 8 parts by mass or more, and is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 300 parts by mass is preferred, 3 to 100 parts by mass is more preferred, 5 to 100 parts by mass is even more preferred, and 8 to 50 parts by mass is particularly preferred. By setting the content at or above the lower limit, blue light transmission is suppressed and light-blocking properties tend to be enhanced. By setting the content at or below the upper limit, a color tone close to black tends to be achieved.

[0390] When the photosensitive resin composition contains an organic black pigment, its content is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 20% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less, based on the total solid content of the photosensitive resin composition. The upper and lower limits can be arbitrarily combined. For example, 3 to 60% by mass is preferred, 5 to 60% by mass is more preferred, 10 to 50% by mass is more preferred, and 20 to 40% by mass is particularly preferred. By setting the content at or above the lower limit, light-blocking properties tend to be improved. Setting the content below the upper limit allows the amount of dispersant to be reduced, which tends to suppress surface roughness.

[0391] When the photosensitive resin composition contains an organic black pigment represented by formula (A1), its content is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 20% by mass or more, and is 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, 3 to 50% by mass is preferred, 5 to 40% by mass is more preferred, 10 to 30% by mass is more preferred, and 20 to 30% by mass is particularly preferred. By setting the content at or above the lower limit, light-blocking properties tend to be improved. Setting the content below the upper limit allows the amount of dispersant to be reduced, which tends to suppress surface roughness.

[0392] When the photosensitive resin composition contains carbon black as an inorganic black pigment, its content is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the photosensitive resin composition. It is also preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass. By setting it to the above lower limit or more, light-shielding properties tend to be enhanced. By setting it to the above upper limit or less, it tends to be possible to form a cured product with high resistance and low dielectric constant.

[0393] When the (a) colorant contains a black pigment and an organic color pigment, the total content ratio thereof is not particularly limited, but the total content ratio of the black pigment and the organic color pigment relative to the total mass of the (a) colorant is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more. Furthermore, it is usually 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 10 to 100% by mass is preferred, 20 to 100% by mass is more preferred, and 30 to 100% by mass is even more preferred. Setting the content at or above the lower limit tends to improve light-blocking properties and enable a color tone close to black. Setting the content at or below the upper limit tends to reduce residue during development and improve reliability during device fabrication.

[0394] The content of (b) alkali-soluble resin is not particularly limited, but is typically 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total solids content of the photosensitive resin composition of the present invention. It is typically 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 55% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 80% by mass is preferred, 10 to 70% by mass is more preferred, 20 to 60% by mass is even more preferred, 30 to 60% by mass is even more preferred, 30 to 55% by mass is particularly preferred, and 40 to 55% by mass is particularly preferred. By setting the content at or above the lower limit, a decrease in the solubility of unexposed areas in a developer tends to be suppressed, and development defects tend to be suppressed. By setting the content at or below the upper limit, appropriate sensitivity can be maintained, dissolution of exposed areas in a developer can be suppressed, and a decrease in pattern sharpness and adhesion tends to be suppressed.

[0395] The content of the alkali-soluble resin (b-1) is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly 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. It is usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 80% by mass is preferred, 10 to 70% by mass is more preferred, 20 to 60% by mass is even more preferred, 20 to 50% by mass is even more preferred, and 30 to 50% by mass is particularly preferred. By setting the content at or above the lower limit, gas barrier properties tend to be improved. By setting the content at or below the upper limit, patterning properties tend to be improved.

[0396] The content of the alkali-soluble resin (b-1) relative to the total mass of the alkali-soluble resin (b) is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, and particularly preferably 70% by mass or more, and is usually 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 20 to 100% by mass is preferred, 30 to 90% by mass is more preferred, 35 to 80% by mass is even more preferred, 50 to 80% by mass is even more preferred, and 60 to 80% by mass is particularly preferred. By setting the content at or above the lower limit, gas barrier properties tend to be improved. By setting the content at or below the upper limit, patterning properties tend to be improved.

[0397] The content of the (c) photopolymerization initiator is not particularly limited, but is typically 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the total solids content of the photosensitive resin composition. It is typically 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less. The upper and lower limits can be arbitrarily combined. For example, 0.1 to 15% by mass is preferred, 0.5 to 15% by mass is more preferred, 1 to 10% by mass is even more preferred, 2 to 8% by mass is even more preferred, and 3 to 6% by mass is particularly preferred. By setting the content at or above the lower limit, sensitivity degradation tends to be suppressed. By setting the content at or below the upper limit, degradation of the solubility of unexposed areas in the developer is suppressed, and development defects tend to be suppressed.

[0398] When a polymerization accelerator is used together with the (c) photopolymerization initiator, the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more, usually 10% by mass or less, and preferably 5% by mass or less, based on the total solids content of the photosensitive resin composition. For example, it is preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass or less. Furthermore, the polymerization accelerator is preferably used in an amount of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass, based on 100 parts by mass of the (c) photopolymerization initiator. By setting the content of the polymerization accelerator at or above the lower limit, a decrease in sensitivity to exposure light tends to be suppressed. By setting the content at or below the upper limit, a decrease in the solubility of the unexposed portion in the developer tends to be suppressed, and development defects tend to be suppressed.

[0399] (c) When a sensitizing dye is used together with the photopolymerization initiator, the content of the sensitizing dye is not particularly limited, but from the viewpoint of sensitivity, it is usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total solid content in the photosensitive resin composition.

[0400] The content of the (d) ethylenically unsaturated compound is not particularly limited, but is typically 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total solids content of the photosensitive resin composition of the present invention. It is also typically 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less. The upper and lower limits can be arbitrarily combined. For example, 1 to 30% by mass is preferred, 5 to 20% by mass is more preferred, and 10 to 20% by mass is even more preferred. By ensuring that the content is at or above the lower limit, proper sensitivity can be maintained, dissolution of exposed areas by the developer can be suppressed, and a decrease in pattern sharpness and adhesion can be suppressed. By ensuring that the content is at or below the upper limit, increased penetration of the developer into exposed areas can be suppressed, which tends to facilitate the production of good images.

[0401] The photosensitive resin composition of the present invention can be prepared by using the solvent (e) so that the total solid content is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the composition can be prepared so that the total solid content is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, and even more preferably 15% by mass to 25% by mass.

[0402] When the photosensitive resin composition contains a dispersant (f), the content of the dispersant (f) is not particularly limited, but is typically 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, relative to the total solid content of the photosensitive resin composition, and is typically 20% by mass or less, preferably 15% by mass or less, 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 preferred, 2 to 15% by mass is more preferred, 3 to 10% by mass is more preferred, and 3 to 7% by mass is particularly preferred. By setting the content at or above the lower limit, sufficient dispersibility tends to be easily obtained. By setting the content at or below the upper limit, surface roughness of the electrode surface tends to be suppressed.

[0403] When the photosensitive resin composition contains (a) a colorant and (f) a dispersant, the content ratio of (f) a dispersant relative to 100 parts by mass of (a) a colorant is not particularly limited, but is usually 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, and is usually 50 parts by mass or less, particularly preferably 30 parts by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 50 parts by mass is preferred, 10 to 50 parts by mass is more preferred, and 15 to 30 parts by mass is even more preferred. By setting the content at or above the lower limit, sufficient dispersibility tends to be easily obtained. By setting the content at or below the upper limit, surface roughness of the electrode surface tends to be suppressed.

[0404] The content ratio of (b) alkali-soluble resin relative to 100 parts by mass of (d) ethylenically unsaturated compound is not particularly limited, but is typically 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 250 parts by mass or more, even more preferably 300 parts by mass or more, and particularly preferably 350 parts by mass or more. It is also typically 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 450 parts by mass or less, and even more preferably 400 parts by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 100 to 700 parts by mass is preferred, 200 to 700 parts by mass is more preferred, 250 to 500 parts by mass is even more preferred, 250 to 450 parts by mass is even more preferred, and 250 to 400 parts by mass is particularly preferred. Setting the content at or above the lower limit tends to result in an appropriate dissolution and development state without peeling, etc. Setting the content at or below the upper limit tends to result in an appropriate dissolution time in the developer.

[0405] The content of the alkali-soluble resin (b-1) relative to 100 parts by mass of the (d) ethylenically unsaturated compound is not particularly limited, but is typically 50 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, even more preferably 200 parts by mass or more, and particularly preferably 240 parts by mass or more. It is also typically 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 50 to 700 parts by mass is preferred, 100 to 500 parts by mass is more preferred, 150 to 400 parts by mass is even more preferred, 200 to 300 parts by mass is even more preferred, and 240 to 300 parts by mass is particularly preferred. By setting the content at or above the lower limit, gas barrier properties tend to improve. By setting the content below the upper limit, patterning properties tend to improve.

[0406] When an adhesion improver is used, its content is not particularly limited, but is usually 0.1 to 5 mass %, preferably 0.2 to 3 mass %, and more preferably 0.4 to 2 mass %, based on the total solid content of the photosensitive resin composition. By setting the content at or above the lower limit, it tends to be possible to sufficiently obtain the effect of improving adhesion. By setting the content at or below the upper limit, it tends to be possible to prevent a decrease in sensitivity and defects caused by residue remaining after development.

[0407] When a surfactant is used, its content is not particularly limited, but is usually 0.001 to 10 mass%, preferably 0.005 to 1 mass%, more preferably 0.01 to 0.5 mass%, and most preferably 0.03 to 0.3 mass%, relative to the total solid content of the photosensitive resin composition. By ensuring that the content is equal to or greater than the lower limit, the smoothness and uniformity of the coating film tend to be readily apparent. By ensuring that the content is equal to or less than the upper limit, the smoothness and uniformity of the coating film tend to be readily apparent, and deterioration of other properties also tends to be suppressed.

[0408] <Method for producing photosensitive resin composition> The photosensitive resin composition of the present invention is produced by a conventional method. Usually, when the photosensitive resin composition of the present invention contains (a) a colorant, the (a) colorant is preferably previously subjected to a dispersion treatment using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. The dispersion treatment results in the (a) colorant being microparticulated, thereby improving the coating properties of the resist.

[0409] The dispersion treatment is preferably carried out in a system that uses in combination (a) a colorant, (e) a solvent, and (f) a dispersant, as well as part or all of (b) an alkali-soluble resin (hereinafter, the composition obtained by the dispersion treatment may be referred to as a "pigment dispersion.") In particular, using a polymer dispersant as the (f) dispersant is preferred because it inhibits the resulting pigment dispersion and photosensitive resin composition from thickening over time, i.e., it provides excellent dispersion stability.

[0410] In this way, in the step of producing a photosensitive resin composition, it is preferable to produce a pigment dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive resin composition can be preferably used. In addition, as the content ratio of each colorant (a) in the pigment dispersion, those described as the content ratio when the photosensitive resin composition of the present invention contains the (a) colorant can be preferably used.

[0411] When a dispersion treatment is performed on a liquid containing all the components to be blended into the photosensitive resin composition, the heat generated during the dispersion treatment may cause denaturation of highly reactive components. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant. When dispersing the (a) colorant using a sand grinder, glass beads or zirconia beads with a particle size of approximately 0.1 to 8 mm are preferably used. Regarding dispersion conditions, the temperature is typically between 0°C and 100°C, preferably between room temperature and 80°C. The optimum dispersion time varies depending on the liquid composition and the size of the dispersion treatment device, and should be adjusted accordingly. A guideline for dispersion is to control the gloss of the pigment dispersion so that the 20° specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300. When the gloss of the photosensitive resin composition is low, the dispersion treatment is often insufficient, leaving coarse pigment (colorant) particles, which can result in insufficient developability, adhesion, resolution, and other properties. If the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be crushed, producing a large number of ultrafine particles, which tends to actually impair dispersion stability.

[0412] The particle size of the pigment dispersed in the pigment dispersion is usually 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method. Next, the pigment dispersion obtained by the above dispersion treatment is mixed with the other components contained in the photosensitive resin composition to obtain a uniform solution or dispersion. Since fine dust particles may be mixed into the liquid during the production process of the photosensitive resin composition, it is desirable to filter the obtained photosensitive resin composition using a filter or the like.

[0413] [Cured product] The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The cured product obtained by curing the photosensitive resin composition of the present invention can be suitably used as a partition wall.

[0414] [Bulkhead] The photosensitive resin composition of the present invention can be suitably used for forming partition walls, particularly partition walls for separating organic layers of organic electroluminescent devices. Examples of organic layers used in organic electroluminescent devices include organic layers used as hole injection layers, hole transport layers, or hole transport layers on hole injection layers, as described in JP 2016-165396 A. Next, the partition walls using the photosensitive resin composition of the present invention will be described in accordance with the method for producing the same.

[0415] (1) Support The material of the support for forming the partition walls is not particularly limited as long as it has adequate strength. A substrate is mainly used. Examples of substrate materials 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 types of glass. Among these, glass and heat-resistant resins are preferred from the viewpoint of heat resistance. 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-mentioned substrates, the substrate can also be formed on a TFT array.

[0416] If necessary, the substrate may be subjected to, for example, corona discharge treatment, ozone treatment, or thin film formation treatment using a silane coupling agent or various resins such as urethane resins in order to improve surface properties such as adhesiveness. The thickness of the substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film of various resins is formed, the thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

[0417] (2) Bulkhead The photosensitive resin composition of the present invention is used for the same purposes as known photosensitive resin compositions for color filters. Hereinafter, the case where the composition is used as a partition wall will be described in accordance with a specific example of a method for forming a partition wall using the photosensitive resin composition of the present invention. Typically, a photosensitive resin composition is applied in the form of a film or a pattern onto a substrate on which partition walls are to be formed by a method such as coating, and the solvent is dried. Subsequently, a pattern is formed by a method such as photolithography, which involves exposure and development. Thereafter, partition walls are formed on the substrate by performing additional exposure or heat curing treatment as necessary.

[0418] (3) Formation of partitions [1] Supply method to the board The photosensitive resin composition of the present invention is usually applied to a substrate in a dissolved or dispersed state in a solvent. The application method can be a conventionally known method, such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. Alternatively, the composition may be applied in a pattern by, for example, an inkjet method or a printing method. Among these, the die coating method is preferred from an overall viewpoint, since it significantly reduces the amount of coating solution used, is completely free from the influence of mist or the like that adheres when using a spin coating method, and suppresses the generation of foreign matter.

[0419] The amount of coating varies depending on the application, but in the case of barrier ribs, for example, the coating is usually applied so that the dry film thickness is 0.5 μm to 10 μm, 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 barrier ribs is uniform across the entire substrate. By minimizing the variation, the light-emitting layer can be formed uniformly, and display defects during light emission can be suppressed.

[0420] When partition walls having different heights are formed at once by photolithography using the photosensitive resin composition of the present invention, the heights of the partition walls finally formed will be different. The substrate may be a known substrate such as a glass substrate, an array substrate, etc. The substrate surface is preferably flat.

[0421] [2] Drying method After the photosensitive resin composition is applied to the substrate, it is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. A reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without increasing the temperature may also be used in combination. Drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. Drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40°C to 130°C, and preferably within the range of 30 seconds to 3 minutes at a temperature of 50°C to 110°C, depending on the type of solvent component, the performance of the dryer used, etc.

[0422] [3] Exposure method Exposure is carried out by superimposing a negative mask pattern on the coating film of the photosensitive resin composition and irradiating the film with a light source of ultraviolet or visible light through this mask pattern. When exposure is carried out using an exposure mask, the exposure mask may be placed close to the coating film of the photosensitive resin composition, or the exposure mask may be placed at a position away from the coating film of the photosensitive resin composition and exposure light may be projected through the exposure mask. A scanning exposure method using laser light without using 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, exposure may be carried out in a deoxygenated atmosphere, or after forming an oxygen-blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

[0423] In a preferred embodiment of the present invention, when partition walls of different heights are simultaneously formed by photolithography, for example, an exposure mask is used that has a light-shielding portion (light transmittance 0%) and a plurality of openings, each of which has a lower average light transmittance (intermediate-transmittance openings) than the opening with the highest average light transmittance (full-transmittance openings). This method causes a difference in the remaining film rate due to the difference in average light transmittance between the intermediate-transmittance openings and the full-transmittance openings, i.e., the difference in exposure dose.

[0424] A known method for creating the intermediate transmission aperture is to use a matrix-shaped light-shielding pattern having minute polygonal light-shielding units, while another known method is to use a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material as the absorber to control the light transmittance. The light source used for the 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 using light of a specific wavelength, an optical filter can also be used.

[0425] The optical filter may be, for example, a thin film type capable of controlling the light transmittance at the exposure wavelength, and in this case, examples of the material include Cr compounds (such as oxides, nitrides, oxynitrides, and fluorides of Cr), MoSi, Si, W, and Al. The exposure dose is not particularly limited, but is usually 1 mJ / cm 2 or more, preferably 5 mJ / cm 2 More preferably, 10 mJ / cm 2 or more, typically 300mJ / cm 2 Less than or equal to 200 mJ / cm 2 or less, more preferably 150 mJ / cm 2 The following is the result.

[0426] In the case of the proximity exposure method, the distance between the object to be exposed and the mask pattern is not particularly limited, but is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and is usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[0427] [4] Development method After the exposure, an image pattern can be formed on the substrate 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.

[0428] Examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; 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, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be a mixture of two or more types.

[0429] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkylbetaines and amino acids.

[0430] Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. The organic solvents may be used alone or in combination with water or an aqueous solution of an alkaline compound. The conditions for the development treatment are not particularly limited, and the development temperature is usually 10 to 50° C., preferably 15 to 45° C., and more preferably 20 to 40° C. The development method can be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.

[0431] [5] Post-exposure and heat-hardening treatment If necessary, the developed substrate may be subjected to additional exposure using a method similar to the above-mentioned exposure method. After development or additional exposure, a thermal curing treatment (also called baking) may be performed. The thermal curing conditions are preferably a temperature of 100°C to 280°C, more preferably 150°C to 250°C, and a time of 5 to 60 minutes. When the present invention is used as a partition wall, the size, shape, etc. are appropriately adjusted depending on the specifications of the organic electroluminescent device to which it is applied, but the height of the partition wall formed from the photosensitive resin composition of the present invention is usually about 0.5 to 10 μm.

[0432] [Organic electroluminescent device] The organic electroluminescent device of the present invention includes a cured product, such as a partition wall, made of the above-described photosensitive resin composition. For example, various organic electroluminescent devices are manufactured using a substrate having a partition wall pattern manufactured by the above-described method. Although the method for forming the organic electroluminescent device is not particularly limited, the organic electroluminescent device is preferably manufactured by forming a partition wall pattern on a substrate by the above-described method, and then forming organic layers such as pixels by a vapor deposition method in which a functional material is sublimated in a vacuum and deposited in the area surrounded by the partition walls on the substrate to form a film, or by a wet process such as a casting method, a spin coating method, or an inkjet printing method.

[0433] The types of organic electroluminescent devices include bottom emission types and top emission types. A bottom-emission type is fabricated, for example, by forming a partition wall on a glass substrate on which a transparent electrode is laminated, and then laminating a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in an opening surrounded by the partition wall, whereas a top-emission type is fabricated, for example, by forming a partition wall on a glass substrate on which a metal electrode layer is laminated as a reflective layer, and then laminating an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the partition wall.

[0434] The light-emitting layer may be an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 or Japanese Patent No. 5734681. Alternatively, quantum dots as described in Japanese Patent No. 5653387 or Japanese Patent No. 5653101 may be used. The layer structure is not limited to this, and for example, each of the hole transport layer and the electron transport layer may have a laminate structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

[0435] The organic electroluminescent element may be formed with each RGB color separated for each opening, or two or more colors may be laminated in one opening. The organic electroluminescent element may have a sealing layer to improve reliability. The sealing layer has the function of preventing moisture in the air from being adsorbed onto the organic electroluminescent element and reducing luminous efficiency. The organic electroluminescent element may have a low-reflection film at the interface with air to improve light extraction efficiency. By disposing the low-reflection film at the interface between air and the element, it is expected that the refractive index gap will be reduced and reflection at the interface will be suppressed. For example, moth-eye structure and super multilayer film technology can be applied to such a low-reflection film.

[0436] When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from the light-emitting layer of a pixel from leaking to other pixels. Furthermore, when electrodes or the like are made of metal, it is necessary to prevent deterioration 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 addition, since it is necessary to provide electrodes on the upper and lower surfaces of the partition walls in an organic electroluminescent device, the partition walls preferably have high resistance and low dielectric constant from the viewpoint of insulating properties. 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.

[0437] [Image display device] The image display device of the present invention can include an organic EL display device having a partition wall or an organic electroluminescent element containing the cured product of the present invention. The organic EL display device is not particularly limited in type or structure as an image display device as long as it includes the above-mentioned organic electroluminescent elements, and can be assembled, for example, by a conventional method using active-drive organic electroluminescent elements. For example, it can be formed by a method such as that described in "Organic EL Display" (Ohmsha, published August 20, 2004, by Tokito Shizuo, Adachi Chinaya, and Murata Hideyuki). For example, an image can be displayed by combining an organic electroluminescent element that emits white light with a color filter, or by combining organic electroluminescent elements that emit different colors such as RGB.

[0438] [illumination] The organic electroluminescent device containing the cured product of the present invention can be used for lighting. There are no particular limitations on the type or structure of the lighting, and it can be assembled according to a conventional method using the organic electroluminescent device containing the cured product of the present invention. The organic electroluminescent device may be of a simple matrix drive type or an active matrix drive type.

[0439] In order to make the illumination emit white light, an organic electroluminescent element that emits white light may be used. Alternatively, organic electroluminescent elements that emit different colors may be combined to mix the colors to produce white, or the color mixing ratio may be adjusted to provide a color adjustment function. [Example]

[0440] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The components of the photosensitive resin compositions used in the following examples and comparative examples and the methods for evaluating them are as follows:

[0441] <Alkali-soluble resin-I> 300 parts by weight of Nippon Kayaku "XD1000" (polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252), 87 parts by weight of acrylic acid, 0.2 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and 255 parts by weight of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 100°C until the acid value reached 3.0 mgKOH / g. Next, 145 parts by weight of tetrahydrophthalic anhydride was added, and the reaction was continued at 120°C for 4 hours. The weight-average molecular weight (Mw) of the resulting alkali-soluble resin-I, as measured by GPC, was 2600, and the acid value was 106 mgKOH / g.

[0442] <Alkali-soluble resin-II>

[0443] [ka]

[0444] 50.0 parts by mass of an epoxy compound having the chemical structure represented by the above formula, 170.3 parts by mass of propylene glycol monomethyl ether acetate, 0.89 parts by mass of 2,4,6-trisdimethylaminomethylphenol, and 0.050 parts by mass of p-methoxyphenol were stirred while purging with nitrogen and heated to 100°C. 44.3 parts by mass of methacrylic acid were added dropwise over 30 minutes. The mixture was further reacted at 100°C for 8 hours until the acid value reached 10 mgKOH / g or less, yielding epoxy (meth)acrylate solution A.

[0445] [ka]

[0446] 50.0 parts by weight of epoxy (meth)acrylate solution A (solids concentration 35.4% by weight) containing the epoxy (meth)acrylate compound of the above chemical structure and 3.1 parts by weight of propylene glycol monomethyl ether acetate were stirred under nitrogen substitution. 3.48 parts by weight of pyromellitic dianhydride (PDMA) and 2.36 parts by weight of phthalic anhydride were added, the temperature was raised to 80°C, and the reaction was carried out for 5 hours to obtain alkali-soluble resin-II with a solids content of 40% by weight, an acid value of 114 mg KOH / g, and a weight-average molecular weight (Mw) of 2544 in terms of polystyrene measured by GPC.

[0447] <Alkali-soluble resin-III> 50.0 parts by mass of epoxy (meth)acrylate solution A (solid content concentration 35.4% by mass), 3.43 parts by mass of trimellitic anhydride, and 7.7 parts by mass of propylene glycol monomethyl ether acetate were stirred while purging with nitrogen, heated to 80°C, and reacted for 2 hours. Subsequently, 5.55 parts by mass of toluene diisocyanate was added, and the reaction was continued at 80°C for 5 hours to obtain alkali-soluble resin-III having a solid content of 40% by mass, an acid value of 75 mgKOH / g, and a weight average molecular weight (Mw) of 2834 in terms of polystyrene measured by GPC.

[0448] <Alkali-soluble resin-IV> 50.0 parts by weight of epoxy (meth)acrylate solution A (solids concentration 35.4% by weight) containing the epoxy (meth)acrylate compound of the above chemical structure, 2.45 parts by weight of trimellitic anhydride, and 4.3 parts by weight of propylene glycol monomethyl ether acetate were stirred while purging with nitrogen, heated to 80°C, and reacted for 2 hours. Subsequently, 2.77 parts by weight of toluene diisocyanate and 1.90 parts by weight of phenyl isocyanate were added, and the reaction was continued at 80°C for 5 hours to obtain alkali-soluble resin-IV with a solids content of 40% by weight, an acid value of 58 mg KOH / g, and a weight average molecular weight (Mw) of 1335 in terms of polystyrene measured by GPC.

[0449] <Alkali-soluble resin-V> 50.0 parts by weight of epoxy (meth)acrylate solution A (solids concentration 35.4% by weight) containing the epoxy (meth)acrylate compound of the above chemical structure and 4.3 parts by weight of propylene glycol monomethyl ether acetate were stirred while purging with nitrogen. 2.77 parts by weight of toluene diisocyanate and 1.90 parts by weight of phenyl isocyanate were added, and the mixture was heated to 80°C and reacted for 5 hours. 2.45 parts by weight of trimellitic anhydride was then added and reacted at 80°C for 2 hours to obtain alkali-soluble resin-V with a solids content of 40% by weight, an acid value of 58 mg KOH / g, and a weight average molecular weight (Mw) of 1095 (measured by GPC) in terms of polystyrene.

[0450] <Alkali-soluble resin-VI> This alkali-soluble acrylic copolymer resin is made by adding an equal amount of acrylic acid to glycidyl methacrylate in a copolymer resin composed of dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.30 / 0.10 / 0.60) and then adding 0.39 moles of tetrahydrophthalic anhydride to each mole of the copolymer resin. Measured by GPC, the weight-average molecular weight (Mw) in terms of polystyrene is 9000, and the acid value of the solid content is 80 mgKOH / g.

[0451] <Pigment-I> Irgaphor (registered trademark) Black S 0100 CF manufactured by BASF (having a chemical structure represented by the following formula (A2))

[0452] [ka]

[0453] <Dispersant-I> This methacrylic AB diblock copolymer consists of an A block containing a repeating unit having a solvent-philic group and a B block containing a repeating unit having a pigment-adsorbing group. It has repeating units of the following formulae (h) to (n). The amine value is 70 mg KOH / g. The weight-average molecular weight before quaternization of the amino groups is 9,000.

[0454] The content ratios of the repeating units of the following formulae (h) to (n) in all repeating units are (h) 33.3 mol%, (i) 13.3 mol%, (j) 6.7 mol%, (k) 6.7 mol%, (l) 6.7 mol%, (m) 24.0 mol%, and (n) 9.3 mol%, respectively.

[0455] [ka]

[0456] [ka]

[0457] <Solvent-I> PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II> MB: 3-methoxy-1-butanol <Photopolymerization initiator-I> Oxime ester photopolymerization initiator with the following chemical structure

[0458] [ka]

[0459] <Ethylenically unsaturated compounds> DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Surfactant> DIC Megafack F-559 <Additives> PM21: Nippon Kayaku Co., Ltd.

[0460] <Gas barrier property evaluation> (Preparation of coating solution for overcoat layer) Each component was added so that the solid content of each component in the total solid content was 48 mass% for alkali-soluble resin-VI, 48 mass% for photopolymerizable compound-I, 3 mass% for photopolymerization initiator-II, 0.1 mass% for surfactant-I, and 0.5 mass% for additive-I, and PGMEA was further added so that the total solid content was 19 mass%, followed by stirring and dissolution to prepare a coating liquid for the overcoat layer.

[0461] (Creating a substrate for the overcoat layer) The overcoat layer coating solution was applied to a glass substrate using a spin coater so that the thickness after heat curing (post-baking) would be 2.0 μm. The coating was then dried in a vacuum dryer for 60 seconds. Subsequently, the coating was heated and dried on a hot plate heated to 100°C for 100 seconds. The resulting coating film was exposed to light at a dose of 60 mJ / cm using an exposure mask with an unshielded area of ​​16 mm x 6 mm. 2 The exposure intensity at a wavelength of 365 nm was 37.5 mW / cm 2 It was. Subsequently, shower development was carried out using an aqueous solution of TMAH (tetramethylammonium hydroxide) at a water pressure of 0.05 MPa at 24° C. for 40 seconds, after which the developer was rinsed with pure water to stop the development, and the film was washed with a water spray for 20 seconds. This substrate was post-baked at 230°C for 30 minutes to obtain a 16mm x 6mm overcoat layer substrate. The resulting overcoat layer substrate is shown in Figure 1 as 1-1 and in Figure 2 as 2-1.

[0462] (Preparation of substrate for measuring gas barrier properties) The photosensitive resin composition of each Example and Comparative Example was applied to the overcoat layer substrate obtained above using a spin coater so that the thickness after heat curing (post-baking) would be 1.5 μm. The resin composition was then dried by heating on a hot plate at 100°C for 100 seconds, and the resulting coating was exposed to light at an exposure dose of 40 mJ / cm without using a mask. 2 The intensity at a wavelength of 365 nm was 37.5 mW / cm 2 It was. Next, using a developer consisting 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), shower development was carried out at 24°C with a water pressure of 0.05 MPa for 65 seconds, after which the developer was rinsed with pure water to stop the development, and the sample was washed with a water rinse spray for 10 seconds. The substrates were post-baked in an oven at 230°C for 30 minutes to obtain substrates for measuring gas barrier properties with a cured film of the photosensitive resin composition for each Example and Comparative Example. The obtained substrates for measuring gas barrier properties are shown in 1-2 in Figure 1 and 2-2 in Figure 2.

[0463] (Gas barrier property measurement) For reference, the overcoat layer substrate was cut to 20 mm x 10 mm so as to include the entire 16 mm x 6 mm overcoat layer, and three substrates were prepared. Similarly, the gas barrier property measurement substrate was cut to 20 mm x 10 mm so as to include the entire 16 mm x 6 mm overcoat layer, and three substrates were prepared for each Example and Comparative Example. The resulting gas barrier property measurement substrates are shown in 1-3 in Figure 1 and 2-3 in Figure 2.

[0464] Three of the prepared overcoat layer substrates and three of the substrates for measuring gas barrier properties from each Example and Comparative Example were heated together at 230°C for 30 minutes in a TG heating furnace (NETZSCH, product name "STA 2500 Regulus"), and the fumes emitted were analyzed using GC (Agilent Technologies, product name "8890") and MS (JEOL, product name "JMS-Q1500"). Among the detected peaks, those attributable only to the overcoat substrate were those that were easily decomposed and detected by heat treatment. The sum of the areas of the peaks represented by the following structural formula (hereinafter referred to as related peaks) contained in the acrylic copolymer resin in the overcoat layer was calculated.

[0465] [ka]

[0466] The sum of the peak areas of the substrates for measuring gas barrier properties was divided by the sum of the peak areas of the substrates for forming the overcoat layer for normalization.

[0467] (Gas barrier evaluation criteria) When the outgassing amount of the overcoat layer substrate is taken as 1, a smaller normalized outgassing amount of the substrate for measuring gas barrier properties indicates higher gas barrier properties. ○: Outgassing normalized value is 0.8 or less ×: The normalized outgassing value exceeds 0.8

[0468] <Evaluation of development solubility> The photosensitive resin composition of each Example and Comparative Example was applied to a 0.7 mm thick glass substrate with an indium tin oxide (ITO) film formed on its surface using a spinner so that the thickness after heat curing (post-baking) would be 1.5 μm. The coating was then dried in a vacuum dryer for 60 seconds. The coating was then heated and dried for 100 seconds on a hot plate heated to 100°C to obtain a coated substrate. The obtained coated substrate was exposed using a photomask. A Canon mirror projection type exposure machine (MPA-600FA) was used, and exposure was performed for 20 seconds so that the exposure amount was 80 mJ / cm2. The illuminance was 500 mW / cm2. The photomask used was a mask with lattice-shaped openings (having 50 μm square covered areas and having multiple covered areas separated by 50 μm exposed areas). Next, using a developer consisting 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), shower development was performed at 24°C under a water pressure of 0.05 MPa, after which the developer was rinsed with pure water to stop the development, and the sample was washed with a water spray for 10 seconds. The time (dissolution time) from the start of resin composition development until the photosensitive resin composition portion corresponding to the square light-shielding portion was dissolved and removed was measured. ◎: Development dissolution time is 20 seconds or more ○: Development dissolution time is 5 seconds or more and less than 20 seconds

[0469] <Preparation of pigment dispersion 1> The pigment, dispersant, alkali-soluble resin, and solvent shown in Table 1 were mixed in the mass ratio shown in Table 1. This mixture was subjected to a dispersion treatment using a paint shaker at a temperature range of 25 to 45°C for 3 hours. Zirconia beads with a diameter of 0.5 mm were used, and 2.5 times the mass of the dispersion was added. After dispersion was completed, the beads and dispersion were separated using a filter to prepare pigment dispersion 1. The amount of solvent in Table 1 includes the amount of solvent derived from the dispersant and alkali-soluble resin.

[0470] [Table 1]

[0471] [Examples 1 to 5, Comparative Example 1] Each component was added so that the solid content of each component in the total solid content was the value shown in Table 2, and PGMEA was added so that the content of MB in the total solvent was 20 mass% and the content of the total solid content was 17 mass%, followed by stirring and dissolution to prepare the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2. The evaluation results of gas barrier property and development solubility measured by the above-mentioned methods are also shown in Table 2.

[0472] [Table 2]

[0473] From Examples 1 to 3 in Table 2, it was found that the photosensitive colored resin composition using the alkali-soluble resin (b-1) of the present invention has good gas barrier properties. This is because the alkali-soluble resin (b-1) has strong intermolecular forces derived from isocyanuric rings and urethane groups, so the outgassing components generated from the base are blocked from diffusing in the cured film of the photosensitive colored resin composition, resulting in excellent gas barrier properties. Furthermore, from Examples 1 to 3, it was found that the photosensitive colored resin composition using the alkali-soluble resin (b-1) of the present invention also had a good dissolution time. This is thought to be because the alkali-soluble resin (b-1) has a relatively reduced number of carboxyl groups due to the introduction of urethane groups, which prevents excessive penetration of the developer during development. On the other hand, in Comparative Example 1, the alkali-soluble resin (b-1) of the present invention was not used, and therefore the dissolution time was poor. This is thought to be because the excess carboxyl groups resulted in excessive permeability of the developer during development. [Explanation of symbols]

[0474] 1. Glass substrate 2. Overcoat layer 3. Cured film of photosensitive resin composition

Claims

1. A photosensitive resin composition comprising (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, The photosensitive resin composition is characterized in that the (b) alkali-soluble resin contains an alkali-soluble resin (b-1) having an isocyanuric ring, a (meth)acryloyloxy group, a carboxy group, and a partial structure represented by the following general formula (4): 【Chemical 1】 (In formula (4), * represents a bond.)

2. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (1): 【Chemistry 2】 (In formula (1), R １ , R ２ , R ３ R each independently represents a hydrogen atom or a monovalent organic group. １ , R ２ , R ３ At least one of R has a (meth)acryloyloxy group, １ , R ２ , R ３ At least one of the following has a partial structure represented by general formula (4); １ , R ２ , R ３ At least one of the groups has a carboxy group.

3. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (5): 【Chemistry 3】 (In formula (5), Y １ represents a divalent organic group. * represents a bond.

4. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (6): 【Chemistry 4】 (In formula (6), Y ２ represents a trivalent organic group. * represents a bond.

5. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (7): 【Chemistry 5】 (In formula (7), Y ３ represents a tetravalent organic group. * represents a bond.

6. The photosensitive resin composition according to claim 2, wherein the alkali-soluble resin (b-1) has a partial structure represented by the following general formula (2) or the following general formula (3): 【Chemistry 6】 (In formula (2), R ４ ~R ６ R each independently represents an alkylene group, and the alkylene group may be interrupted by an etheric oxygen atom. ７ ~R ９ Each of the * symbols independently represents a hydrogen atom or a methyl group. * symbol represents a bond, and at least one of the * symbols is bonded to the partial structure represented by general formula (4). 【Chemistry 7】 (In formula (3), R ４ ~R ８ is the same as formula (2). １０ represents an alkyl group which may have a substituent. * represents a bond, and at least one of the *'s is bonded to the partial structure represented by general formula (4).

7. 3. The photosensitive resin composition according to claim 1, further comprising (a) a colorant, wherein the (a) colorant contains an organic color pigment or a black pigment.

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

9. 3. The photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin (b-1) is 10 mass% or more relative to the total mass of the alkali-soluble resin (b).

10. 3. The photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin (b) is 100 parts by mass or more per 100 parts by mass of the ethylenically unsaturated compound (d).

11. 3. The photosensitive resin composition according to claim 1, wherein the optical density of the cured coating film per 1 μm of film thickness is 0.5 or more.

12. The photosensitive resin composition according to claim 1 or 2, which is used for forming partition walls.

13. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.

14. A partition wall comprising the cured product according to claim 13.

15. An organic electroluminescent device comprising the partition wall according to claim 14 .

16. An image display device comprising the partition wall according to claim 14.

Images