Photosensitive coloring composition, cured product, image display device, and pigment dispersion liquid for image display device

Abstract

To provide a photosensitive colored composition excellent in electric reliability after ultraviolet irradiation and having good solvent resistance.SOLUTION: The photosensitive colored composition of the present invention is a photosensitive colored composition comprising (a) a colorant, (b) an alkali-soluble polymer, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a dispersing agent, wherein the optical concentration per 1 μm of the thickness of the cured coating film is 0.5 or more, and the dispersing agent (f) comprises a dispersing agent (f1) having a repeating unit represented by Formula (1). (In the formula (1), Y - is a counter anion represented by the general formula (2). ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive coloring composition, a cured product, an image display device, and a pigment dispersion for the image display device. More specifically, the present invention relates to a photosensitive coloring composition used for forming a colored spacer in an image display device such as a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, and an image display device including the cured product. This application claims priority based on Japanese Patent Application No. 2019-162547 filed on September 6, 2019, and Japanese Patent Application No. 2020-026622 filed on February 19, 2020, the contents of which are incorporated herein by reference. [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. Many of the components that make up LCD cells are formed using photosensitive compositions, typically photolithography. These photosensitive compositions are easy to form into fine structures and are easy to process on substrates for large screens, so their range of application is expected to expand in the future.

[0003] However, LCDs manufactured using photosensitive compositions may not be able to maintain the voltage applied to the liquid crystal due to the electrical properties of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition, which may result in problems such as uneven display. This has a particularly large impact on components closer to the liquid crystal layer in color liquid crystal displays, such as so-called columnar spacers and photospacers used to maintain a constant distance between two substrates in a liquid crystal panel.

[0004] In the past, when a spacer without light-shielding properties was used in a TFT-type LCD, light passing through the spacer could cause the TFT, which acts as a switching element, to malfunction. To prevent this, the use of a spacer with light-shielding properties (colored spacer) has been investigated.

[0005] In recent years, with changes in panel structure, methods have been proposed for forming colored spacers in one go by photolithography. For example, Patent Document 1 discloses a photosensitive coloring composition that is highly reliable, has excellent light-blocking properties, and suppresses the elution of impurities into the solvent, by using multiple types of organic color pigments and a specific photopolymerization initiator in combination.

[0006] Patent Document 2 discloses a coloring composition that has excellent light-blocking properties in the visible light region and excellent transmittance in the near-infrared region by using a specific colorant in combination with a dispersant having an amino group or the like with a specific structure.

[0007] Patent Document 3 discloses that a block copolymer having a specific anion has excellent heat resistance. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2016-164623 [Patent Document 2] Japanese Patent Application Publication No. 2018-169539 [Patent Document 3] International Publication No. 2018 / 079659 Summary of the Invention [Problem to be solved by the invention]

[0009] With recent changes in panel structure, the method of irradiating liquid crystal cells with ultraviolet light after fabrication to improve liquid crystal alignment has become widespread. However, ultraviolet light irradiation tends to decompose some of the pigments contained in colored spacers and other materials, generating impurities. Even in such cases, it is necessary to maintain sufficient electrical reliability.

[0010] The present inventors have investigated the photosensitive coloring composition containing the dispersant described in Patent Document 1, and have found that it is difficult to ensure electrical reliability after ultraviolet irradiation. The photosensitive coloring composition containing a dispersant described in Patent Document 2 had insufficient chemical resistance (NMP resistance) to a solvent (N-methylpyrrolidone, NMP) used when forming an alignment film. With the photosensitive coloring composition containing the dispersant described in Patent Document 3, it was difficult to ensure electrical reliability both before and after ultraviolet irradiation.

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition which has excellent electrical reliability after ultraviolet irradiation and good solvent resistance. [Means for solving the problem]

[0012] As a result of extensive research, the present inventors have found that the above problems can be solved by using a specific dispersant, and have thus completed the present invention. That is, the gist of the present invention is as follows.

[0013] [1] A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more, A photosensitive coloring composition, wherein the dispersant (f) contains a dispersant (f1) having a repeating unit represented by the following general formula (1):

[0014] [ka]

[0015] (In formula (1), R 1 ~R 3 are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 ~R 3 Two or more of these may be bonded to each other to form a ring structure. R 4 is a hydrogen atom or a methyl group. X is a divalent linking group. Y - is a counter anion represented by the following general formula (2):

[0016] [ka]

[0017] (In formula (2), R 5 represents an alkyl group which may have a substituent.

[0018] [2] The photosensitive coloring composition according to [1], wherein the (a) colorant comprises at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment. [3] The photosensitive coloring composition according to [1] or [2], wherein the colorant (a) contains a black pigment. [4] The photosensitive coloring composition according to [3], wherein the black pigment comprises an organic black pigment. [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the content of the colorant (a) is 10% by mass or more based on the total solid content. [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the dispersant (f1) has an amine value of 30 mgKOH / g or more.

[0019] [7] The photosensitive coloring composition according to any one of [1] to [6], which is used for forming a colored spacer. [8] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [7]. [9] An image display device comprising the cured product according to [8].

[0020]

[10] A pigment dispersion for an image display device, comprising: (a) a colorant; (e) a solvent; and (f) a dispersant, the (a) colorant contains a black pigment, A pigment dispersion for an image display device, wherein the (f) dispersant contains a dispersant (f1) having a repeating unit represented by the following general formula (1):

[0021] [ka]

[0022] (In formula (1), R 1 ~R 3 are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 ~R 3 Two or more of these may be bonded to each other to form a ring structure. R 4 is a hydrogen atom or a methyl group. X is a divalent linking group. Y - is a counter anion represented by the following general formula (2):

[0023] [ka]

[0024] (In formula (2), R 5 represents an alkyl group which may have a substituent.

[0025]

[11] The pigment dispersion for an image display device according to

[10] , wherein the black pigment contains an organic black pigment.

[12] The pigment dispersion for an image display device according to

[10] or

[11] , wherein the amine value of the dispersant (f1) is 30 mgKOH / g or more. [Effects of the Invention]

[0026] According to the present invention, it is possible to provide a photosensitive coloring composition that has excellent electrical reliability after ultraviolet irradiation and good solvent resistance. DETAILED DESCRIPTION OF THE INVENTION

[0027] 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".

[0028] The term "(co)polymer" includes both homopolymers and copolymers, and the terms "acid (anhydride)" and "(anhydrous)...acid" include both acids and their anhydrides. 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.

[0029] 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. In the present invention, the term "total solid content" means all components other than the solvent contained in the photosensitive coloring composition or pigment dispersion. 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). 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.

[0030] With respect to pigments, "CI" means Color Index.

[0031] In this specification, percentages and parts expressed by "mass" have the same meaning as percentages and parts expressed by "weight".

[0032] [Photosensitive coloring composition] The photosensitive coloring composition of the present invention comprises: (a) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylenically unsaturated compounds (e) Solvent (f) Dispersant as an essential component, and may further contain other compounding components such as 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, as necessary. Usually, each compounding component is used in a state of being dissolved or dispersed in a solvent.

[0033] <(a) Colorant> The photosensitive coloring composition of the present invention contains (a) a colorant. By containing (a) a colorant, it is possible to obtain appropriate light absorption properties, particularly appropriate light blocking properties when used for forming a light blocking member such as a colored spacer. In addition, the photosensitive coloring composition of the present invention has an optical density per 1 μm of film thickness of the cured coating film (hereinafter, sometimes referred to as "OD per unit film thickness") of 0.5 or more. (a) By containing a colorant and making the OD per unit film thickness equal to or greater than the lower limit, the light-shielding properties of the obtained cured product, particularly the colored spacer, are improved.

[0034] The OD per unit film thickness can be calculated by measuring the optical density and film thickness of the coating film obtained by curing the photosensitive coloring composition, and dividing the optical density by the film thickness. The conditions for producing the coating film are not particularly limited, but for example, the conditions described in the examples below can be adopted. In order to make the OD per unit film thickness equal to or greater than the lower limit, for example, (a) the type of colorant and its content in the total solid content may be appropriately adjusted.

[0035] The type of colorant (a) that can be used in the photosensitive coloring composition of the present invention is not particularly limited, and 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 the pigments, organic color pigments are preferred from the viewpoint of suppressing absorption of ultraviolet light and making it easier to control the shape and step of the cured product, and black pigments are preferred from the viewpoint of light-blocking properties.

[0038] The organic color pigment may be used alone or in combination of two or more. In particular, from the viewpoint of achieving an OD per unit film thickness of 0.5 or more, 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.

[0039] 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.

[0040] 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. Among these, from the viewpoint 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. In terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Red 177, 254, 272. When the photosensitive coloring composition is cured with ultraviolet light, it is preferable to use a red pigment with low ultraviolet absorption rate. From this viewpoint, it is more preferable to use CI Pigment Red 254, 272.

[0041] 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. Among these, from the viewpoint of dispersibility and light-shielding properties, it is preferable to use CI Pigment Orange 13, 43, 64, and 72, and when the photosensitive coloring composition is cured with ultraviolet light, it is preferable to use an orange pigment with low ultraviolet absorption rate, and from this viewpoint, it is more preferable to use CI Pigment Orange 64 and 72.

[0042] 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. Among these, from the viewpoint of light-blocking properties, preferred are CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60, and more preferred is CI Pigment Blue 15:6. In terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Blue 15:6, 16, 60. When the photosensitive coloring composition is cured with ultraviolet light, it is preferable to use a blue pigment with low ultraviolet absorption rate. From this point of view, it is more preferable to use CI Pigment Blue 60.

[0043] 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. Among these, from the viewpoint of light-blocking properties, preferred are CI Pigment Violet 19, 23, and 29, and more preferred is CI Pigment Violet 23. In terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Violet 23 or 29. When the photosensitive coloring composition is cured with ultraviolet light, it is preferable to use a purple pigment with low ultraviolet absorption rate. From this viewpoint, it is more preferable to use CI Pigment Violet 29.

[0044] 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. Of these, CI Pigment Green 7 and 36 are preferred. 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. Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferred, and CI Pigment Yellow 83, 138, 139, 150, and 180 are more preferred.

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

[0046] Among these, from the viewpoint of the light-blocking properties of the cured product and control of the shape and step, 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

[0047] Furthermore, 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. 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] Examples of black pigments include organic black pigments and inorganic black pigments. Of these, organic black pigments are preferred because they suppress ultraviolet absorption and make it easier to control the shape and step of the cured product. Among organic black pigments, from the viewpoint of suppressing a decrease in the voltage holding ratio of the liquid crystal and suppressing ultraviolet light absorption to facilitate control of the shape and step, 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 (1) (hereinafter, sometimes referred to as "compound (1)"), a geometric isomer of compound (1), a salt of compound (1), and a salt of a geometric isomer of compound (1) (hereinafter, sometimes referred to as "organic black pigment represented by general formula (1)").

[0049] [ka]

[0050] In formula (1), 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 , R17 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 joined together by bridges; 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 (1) and the geometric isomers of compound (1) 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 (1) is anionic, it is preferably a salt in which its 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 (1) is anionic, it is preferably a similar salt.

[0054] The following substituents in general formula (1) 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. R 12 , R 14 , R 15 , R 17 , R 19and 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.

[0055] R 11 and R 16 are each independently preferably a hydrogen atom, CH3 or CF3, more preferably a hydrogen atom. Preferably, R 11 and R 16 , R 12 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

[0056] 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.

[0062] The organic black pigment represented by the general formula (1) 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 (2) (hereinafter also referred to as "compound (2)") and a geometric isomer of compound (2).

[0063] [ka]

[0064] An example of such an organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF). 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 (1), particularly a sulfonic acid derivative of compound (2), is present during dispersion, dispersibility and storage stability may be improved, so it is preferable that the organic black pigment contains these sulfonic acid derivatives.

[0065] Examples of organic black pigments other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.

[0066] On the other hand, from the viewpoint of light-blocking 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.

[0067] 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 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 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 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

[0068] 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 is suitable as the resin-coated carbon black. Resin-coated carbon black is preferred in terms of volume resistivity and dielectric constant.

[0069] The carbon black to be subjected to resin coating treatment preferably has a total Na and Ca content of 100 ppm or less. Carbon black typically contains Na, which is mixed in from raw material oil, combustion oil (or gas), reaction stop water, granulation water, and even reactor materials during production, as well as ash composed of Ca, K, Mg, Al, Fe, etc., on the order of percent. Of these, Na and Ca are typically contained in amounts of several hundred ppm or more each, but reducing their content tends to inhibit their penetration into the transparent electrode (ITO) and other electrodes, thereby preventing electrical short circuits.

[0070] Methods for reducing the content of ash containing Na and Ca include carefully selecting raw material oil, fuel oil (or gas), and reaction quench water for producing carbon black that contain as little of these substances as possible, and minimizing the amount of alkaline substances added to adjust the structure. Another method includes washing the carbon black produced in the furnace with water or hydrochloric acid to dissolve and remove the Na and Ca.

[0071] Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, a solvent that is poorly soluble in water is added. The carbon black migrates to the solvent and is completely separated from the water, and most of the Na and Ca present in the carbon black are dissolved in the water or acid and removed. While it may be possible to reduce the total amount of Na and Ca to 100 ppm or less using only the carbon black manufacturing process with carefully selected raw materials or the water or acid dissolution method alone, it is even easier to reduce the total amount of Na and Ca to 100 ppm or less by using both methods in combination.

[0072] Furthermore, the resin-coated carbon black is preferably so-called acidic carbon black with a pH of 6 or less. This is advantageous because the dispersion diameter (agglomerate diameter) in water is small, making it possible to coat even the finest units. Furthermore, the average particle diameter is preferably 40 nm or less, and the dibutyl phthalate (DBP) absorption is preferably 140 ml / 100 g or less. By keeping the values ​​within the above ranges, a coating film with good light-blocking properties tends to be obtained. The average particle diameter refers to the number-average particle diameter, and refers to the circle-equivalent diameter determined by particle image analysis in which photographs taken at tens of thousands of magnifications using an electron microscope are taken of several fields of view, and approximately 2,000 to 3,000 particles in these photographs are counted using an image processing device.

[0073] There are no particular limitations on the method for preparing resin-coated carbon black. For example, after appropriately adjusting the amounts of carbon black and resin, 1. a resin solution obtained by mixing and dissolving the resin in a solvent such as cyclohexanone, toluene, or xylene under heat is mixed with a suspension of carbon black and water, and the mixture is stirred to separate the carbon black and water. The water is then removed and the resulting composition is heated and kneaded to form a sheet, which is then crushed and dried; 2. a resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate the carbon black and resin, and the resulting granules are then separated and heated to remove the remaining solvent. 3. A method in which a carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, the mixture is mixed and dried, the solvent is removed to obtain carboxylic acid-impregnated carbon black, and then a resin is added to this and dry-blended; 4. A method in which a reactive group-containing monomer component that constitutes the resin to be coated and water are stirred at high speed to prepare a suspension, which is polymerized and cooled to obtain a reactive group-containing resin from the polymer suspension, carbon black is added to this and kneaded, the carbon black is reacted with the reactive group (carbon black is grafted), and the suspension is cooled and pulverized; etc. can be employed.

[0074] The type of resin used for the coating treatment is not particularly limited, but synthetic resins are common, and resins having a benzene ring in their structure are preferred from the standpoint of dispersibility and dispersion stability because they have a stronger amphoteric surfactant-like effect. Specific examples of synthetic resins that can be used include thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, as well as thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylene sulfone, polyarylate, and polyetheretherketone. The amount of resin coated on carbon black is preferably 1 to 30% by mass based on the total amount of carbon black and resin. Amounts equal to or greater than the lower limit tend to ensure sufficient coating. Amounts equal to or less than the upper limit tend to prevent adhesion between resins and improve dispersibility.

[0075] Carbon black coated with a resin in this manner can be used as a light-blocking material for colored spacers in a conventional manner, and color filters incorporating these colored spacers as components can be produced in a conventional manner. The use of such carbon black tends to enable the production of colored spacers with high light-blocking efficiency and low surface reflectance at low cost. It is also believed that coating the carbon black surface with a resin also serves to trap Ca and Na within the carbon black.

[0076] These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less, where the average particle size is determined by the number of pigment particles. In the photosensitive coloring 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 coloring 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.

[0077] In addition, in the photosensitive coloring composition of the present invention, colorants such as organic color pigments and black pigments may be used alone or in combination of two or more. Among these, it is preferable to use an organic black pigment and an organic color pigment in combination from the viewpoint of easily controlling the shape and step, while it is preferable to use carbon black and an organic color pigment in combination from the viewpoint of light-shielding properties.

[0078] In addition to the above-mentioned organic color pigments and black pigments, dyes may also be used. Examples of dyes that can be used as coloring materials 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.

[0079] 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. Other examples of phthalocyanine dyes include CI Pad Blue 5; quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9; quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3 and CI Disperse Yellow 64; and nitro dyes include CI Acid Yellow 1, CI Acid Orange 3 and CI Disperse Yellow 42.

[0080] <(b) Alkali-soluble resin> The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it is a resin containing a carboxy group or a hydroxyl group, and examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxy group-containing epoxy resins, carboxy group-containing urethane resins, novolac resins, and polyvinylphenol resins. (b1) Epoxy (meth)acrylate resin (b2) Acrylic copolymer resin These can be used alone or in combination of two or more types.

[0081] <(b1) Epoxy (meth)acrylate resin> (b1) Epoxy (meth)acrylate resins are resins 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. Furthermore, the (b1) epoxy (meth)acrylate resin 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.

[0082] 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 (b1) epoxy (meth)acrylate resin. 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.

[0083] As the epoxy (meth)acrylate resin (b1) used in the present invention, the following epoxy (meth)acrylate resin (b1-1) and / or epoxy (meth)acrylate resin (b1-2) (hereinafter sometimes referred to as "carboxy group-containing epoxy (meth)acrylate resin") are particularly preferably used from the viewpoint of developability and reliability.

[0084] <Epoxy (meth)acrylate resin (b1-1)> 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. <Epoxy (meth)acrylate resin (b1-2)> 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.

[0085] 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. 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.

[0086] Examples of epoxy resins include bisphenol A type epoxy resins (e.g., "jER (registered trademark, the same applies hereinafter) 828," "jER1001," "jER1002," and "jER1004" manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point: 76°C)), and bisphenol F type resins (e.g., " jER807, "EP-4001", "EP-4002", "EP-4004", etc.), 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 resin (for example, "EP PN-201, "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 (for example, "EOCN (registered trademark, the same applies hereinafter)-102S," "EOCN-1020," and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resins (for example, "EPPN (registered trademark)" manufactured by Nippon Kayaku Co., Ltd.), Suitable epoxy resins that can be used include: epoxy resins such as "CELLOXIDE (registered trademark, the same applies hereinafter)-501," "EPPN-502," and "EPPN-503" manufactured by Daicel Corporation; alicyclic epoxy resins ("CELLOXIDE (registered trademark, the same applies hereinafter) 2021P" and "CELLOXIDE EHPE" manufactured by Daicel Corporation; epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (for example, "EXA-7200" manufactured by DIC Corporation and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.); 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).

[0087] [ka]

[0088] In the general formula (B1), a is an average value and represents a number from 0 to 10; 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.

[0089] [ka]

[0090] In the general 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.

[0091] [ka]

[0092] In the above general 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. c represents 2 or 3.

[0093] [ka]

[0094] In the above general formulae (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 having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.

[0095] [ka]

[0096] In the general 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.

[0097] Among these, it is preferable to use an epoxy resin represented by any one of the general formulas (B1) to (B4).

[0098] 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 acrylic acid dimer include 2-(meth)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), and 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. Among these, (meth)acrylic acid is particularly preferred from the viewpoint of sensitivity.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] The use of polyhydric alcohols increases the molecular weight of the (b1) epoxy (meth)acrylate resin, allowing for the introduction of branching into the molecule, which tends to balance the molecular weight and viscosity. It also increases the rate of acid group introduction into the molecule, which tends to make it easier to balance sensitivity, adhesion, and other properties.

[0106] In addition to the above-mentioned carboxyl group-containing epoxy (meth)acrylate resins, for example, those described in Korean Patent Publication No. 10-2013-0022955 can be used.

[0107] 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 10,000 or less, preferably 8,000 or less, and more preferably 7,000 or less. For example, 1,000 to 10,000 is preferred, 1,500 to 10,000 is more preferred, 1,500 to 8,000 is even more preferred, 2,000 to 8,000 is even more preferred, and 2,000 to 7,000 is particularly preferred. By setting the Mw at or above the lower limit, excessive solubility in the developer tends to be suppressed. By setting the Mw at or below the upper limit, good solubility in the developer tends to be achieved.

[0108] The acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 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, even more preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. For example, 10 mgKOH / g to 200 mgKOH / g is preferred, more preferably 20 mgKOH / g to 150 mgKOH / g, even more preferably 40 mgKOH / g to 120 mgKOH / g, and even more preferably 50 mgKOH / g to 100 mgKOH / g. By setting the acid value at or above the lower limit, appropriate development solubility tends to be obtained. By setting the acid value at or below the upper limit, excessive development and film dissolution tend to be suppressed.

[0109] 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 (b1-I) (hereinafter may be abbreviated as "(b1-I) epoxy(meth)acrylate resin") and / or an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (b1-II) (hereinafter may be abbreviated as "(b1-II) epoxy(meth)acrylate resin"):

[0110] [ka]

[0111] In formula (b1-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 (b1-I) may be further substituted with any substituent.

[0112] [ka]

[0113] In formula (b1-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.

[0114] <(b1-I) Epoxy (meth)acrylate resin> First, the epoxy (meth)acrylate resin having the partial structure represented by the general formula (b1-I) will be described in detail.

[0115] [ka]

[0116] In formula (b1-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 (b1-I) may be further substituted with any substituent.

[0117] (R 12 ) In the formula (b1-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.

[0118] The divalent aliphatic group may be linear, branched, or cyclic. Among these, linear groups are preferred from the viewpoint of development solubility. On the other hand, cyclic 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. For example, 1 to 20 is preferred, more preferably 1 to 15, and even more preferably 1 to 10. By setting the carbon number at or above the lower limit, a strong film is easily obtained, surface roughness 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.

[0119] 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. Among these, a methylene group is preferred from the viewpoint of the rigidity of the skeleton. 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. 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. 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 tend to be easily suppressed, and resolution tends to be improved. 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. Among these, from the viewpoint of the rigidity of the skeleton, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred.

[0120] 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. Among these, from the viewpoint of ease of synthesis, an unsubstituted group is preferred.

[0121] Furthermore, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. 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. For example, 4 to 20 is preferred, more preferably 5 to 15, and even more preferably 6 to 10. By setting the number of carbon atoms at or above the lower limit, a strong film tends to be easily obtained, the surface is less likely to become rough, and adhesion to the substrate tends to be good. By setting the number of carbon atoms at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved.

[0122] 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. In addition, the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the 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, each of which has two free valences. Among these, 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.

[0123] 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. Among these, from the viewpoint of solubility in development, unsubstituted groups are preferred.

[0124] Furthermore, 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. 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, surface roughness 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. 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. 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, surface roughness 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.

[0125] 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 (b1-IA) to (b1-IF). Among these, the group represented by the following formula (b1-IA) is preferred from the viewpoints of skeletal rigidity and film hydrophobicity.

[0126] [ka]

[0127] k represents 1 or 2. From the viewpoint of adhesion and patterning properties, k is preferably 1, and from the viewpoint of NMP resistance, k is preferably 2. In addition, the epoxy (meth)acrylate (b1-I) may contain both a partial structure where k is 1 and a partial structure where k is 2.

[0128] As described above, the benzene ring in formula (b1-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. Among these, from the viewpoint of patterning properties, unsubstituted groups are preferred.

[0129] Moreover, the partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1) from the viewpoint of ease of synthesis.

[0130] [ka]

[0131] In formula (b1-I-1), R 11 , R 12 and k are the same as those in formula (b1-I), and R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond. The benzene ring in formula (b1-I-1) may be further substituted with any substituent.

[0132] 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. Among these, 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.

[0133] As described above, the benzene ring in formula (b1-I-1) may be further substituted with any substituent. As the substituent, those exemplified for the benzene ring in formula (b1-I) can be preferably used.

[0134] (b1-I) The partial structure represented by the formula (b1-I-1) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types, and examples thereof include R X is a hydrogen atom, and R X However, polybasic acid residues may be present in the mixture.

[0135] Furthermore, the number of partial structures represented by the formula (b1-I) contained in one molecule of the epoxy (meth)acrylate resin (b1-I) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, even more preferably 15 or less. 1 to 20 is preferred, more preferably 1 to 15, and even more preferably 3 to 15. By ensuring that the number is equal to or greater than the lower limit, a strong film tends to be obtained and surface roughness tends to be less likely to occur. By ensuring that the number is equal to or less than the upper limit, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved.

[0136] The weight average molecular weight (Mw) of the (b1-I) epoxy (meth)acrylate resin, 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 also preferably 30000 or less, more preferably 20000 or less, even more preferably 10000 or less, and particularly preferably 8000 or less. For example, it is preferably 1000 to 30000, more preferably 1500 to 20000, even more preferably 1500 to 10000, even more preferably 1500 to 8000, particularly preferably 2000 to 8000, and particularly preferably 2000 to 7000. By ensuring that it is equal to or greater than the lower limit, the residual film rate of the photosensitive coloring composition tends to be good. By setting the content to the upper limit or less, the resolution tends to be good.

[0137] The acid value of the (b1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, even more preferably 40 mgKOH / g or more, even more preferably 50 mgKOH / g or more, particularly preferably 80 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, particularly preferably 100 mgKOH / g or less. For example, it is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 20 mgKOH / g to 200 mgKOH / g, even more preferably 40 mgKOH / g to 150 mgKOH / g, even more preferably 50 mgKOH / g to 130 mgKOH / g, particularly preferably 80 mgKOH / g to 100 mgKOH / g or less. By setting the content to the lower limit or more, the development solubility is improved and the resolution tends to be good, and by setting the content to the upper limit or less, the film remaining rate of the photosensitive coloring composition tends to be good.

[0138] Specific examples of (b1-I) epoxy (meth)acrylate resins are listed below. In the examples, * indicates a bond.

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] <(b1-II) Epoxy (meth)acrylate resin> Next, the epoxy (meth)acrylate resin having the partial structure represented by the general formula (b1-II) will be described in detail.

[0144] [ka]

[0145] In formula (b1-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.

[0146] (R 14 ) In the general formula (b1-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.

[0147] 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. 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 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. 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. For example, 4 to 40 is preferred, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting the carbon number at or above the lower limit, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By setting the carbon number at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. 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. Among these, an adamantane ring is preferred from the viewpoints of the film remaining rate and resolution of the photosensitive coloring composition.

[0148] On the other hand, the number of rings possessed by 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. 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 making the number equal to or greater than the lower limit, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By making the number equal to or less than the upper limit, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. 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. For example, it is preferably 4 to 40, more preferably 6 to 40, even more preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15. By setting it to the lower limit or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By setting it to the upper limit or less, patterning properties tend to be good. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, 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.

[0149] Furthermore, 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.

[0150] The divalent aliphatic group may be linear, branched, or cyclic. Among these, linear groups are preferred from the viewpoint of development solubility, while cyclic 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. For example, 1 to 25 is preferred, more preferably 3 to 20, and even more preferably 6 to 15. By setting the carbon number at or above the lower limit, a strong film tends to be easily obtained, the surface is less likely to become rough, 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.

[0151] 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. Among these, a methylene group is preferred from the viewpoint of the rigidity of the skeleton. 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. 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. 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 in sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. 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, in which two hydrogen atoms have been removed from the ring. Among these, 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.

[0152] 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. Among these, from the viewpoint of ease of synthesis, an unsubstituted group is preferred.

[0153] Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. 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. For example, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. By setting the number of carbon atoms at or above the lower limit, a strong film tends to be easily obtained, surface roughness is less likely to occur, and adhesion to the substrate tends to be good. By setting the number of carbon atoms at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved.

[0154] 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. In addition, the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the 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, each of which has two free valences. Among these, 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.

[0155] 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. Among these, from the viewpoint of solubility in development, unsubstituted groups are preferred.

[0156] Furthermore, 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. 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, surface roughness 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. 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. 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, surface roughness 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.

[0157] 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 formulae (b1-IA) to (b1-IF). Among these, the group represented by the formula (b1-IC) is preferred from the viewpoints of the rigidity of the skeleton and the hydrophobicity of the film.

[0158] 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.

[0159] (R 15 , R 16 ) In the general formula (b1-II), R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent.

[0160] The divalent aliphatic group may be linear, branched, or cyclic. Among these, linear groups are preferred from the viewpoint of solubility in development, while cyclic 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. For example, 1 to 20 is preferred, more preferably 3 to 15, and even more preferably 6 to 10. By setting the carbon number at or above the lower limit, a strong film tends to be easily obtained, the surface is less likely to become rough, 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 tend to be easily suppressed, and resolution tends to be improved.

[0161] 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. Among these, a methylene group is preferred from the viewpoint of the rigidity of the skeleton. 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. 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. 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 easily suppressed, and resolution tends to be improved. 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. Among these, from the viewpoint of the rigidity of the skeleton, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring or an adamantane ring are preferred.

[0162] 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. Among these, from the viewpoint of ease of synthesis, an unsubstituted group is preferred.

[0163] (m, n) In the general formula (b1-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 tends to be improved and surface roughness 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, it is preferable that m and n are 1 or greater.

[0164] Moreover, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1) from the viewpoint of adhesion to a substrate.

[0165] [ka]

[0166] In formula (b1-II-1), R 13 , R 15 , R 16 , m and n are the same as those in formula (b1-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 (b1-II-1) may be further substituted with any substituent.

[0167] (R α ) In the general formula (b1-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.

[0168] 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. 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 making the number equal to or greater than the lower limit, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By making the number equal to or less than the upper limit, patterning properties tend to be improved. 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. 4 to 40 is preferred, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting the carbon number at or above the lower limit, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By setting the carbon number at or below the upper limit, patterning properties tend to be good. 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. Among these, an adamantane ring is preferred from the viewpoint of strong film properties.

[0169] 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. 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 making the number equal to or greater than the lower limit, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By making the number equal to or less than the upper limit, patterning properties tend to be improved. 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. For example, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. By setting the number of carbon atoms at or above the lower limit, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur, while by setting the number of carbon atoms at or below the upper limit, patterning properties tend to be improved. 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. Among these, a fluorene ring is preferred from the viewpoint of development solubility.

[0170] 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. Of these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0171] 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.

[0172] Among these, R is the best from the viewpoint of strong film hardness. α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

[0173] As described above, the benzene ring in formula (b1-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. Among these, from the viewpoint of patterning properties, unsubstituted groups are preferred.

[0174] Specific examples of the partial structure represented by the formula (b1-II-1) are listed below.

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] Moreover, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-2) from the viewpoints of the rigidity of the skeleton and the hydrophobicity of the film.

[0181] [ka]

[0182] In formula (b1-II-2), R 13 , R 15 , R 16 , m and n are the same as those in formula (b1-II), and R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond. The benzene ring in formula (b1-II-2) may be further substituted with any substituent.

[0183] (R β ) In the formula (b1-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.

[0184] 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. 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 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. 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. For example, 4 to 40 is preferred, more preferably 6 to 35, and even more preferably 8 to 30. 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. Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferred from the viewpoints of film loss during development and resolution.

[0185] On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. 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 making the number equal to or greater than the lower limit, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By making the number equal to or less than the upper limit, deterioration in sensitivity and film loss tend to be easily suppressed, and resolution tends to be improved. 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, still more preferably 20 or less, and particularly preferably 15 or less. For example, it is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15. By setting it to the lower limit or more, a strong film tends to be easily obtained and surface roughness tends to be less likely to occur. By setting it to the upper limit or less, it is easy to suppress deterioration in sensitivity and film loss, and resolution tends to be improved. 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. Among these, a fluorene ring is preferred from the viewpoint of developability.

[0186] 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. Of these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0187] Among these, from the viewpoint of suppressing film loss and 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 characteristics, R β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

[0188] As described above, the benzene ring in formula (b1-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, in which case examples of the substituent include divalent groups such as -O-, -S-, -NH-, and -CH2-. Among these, from the viewpoint of patterning properties, unsubstituted groups are preferred, and from the viewpoint of preventing film loss and the like, methyl group substitution is preferred.

[0189] Specific examples of the partial structure represented by the formula (b1-II-2) are shown below, in which * indicates a bond.

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] [ka]

[0194] The partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoint of the coating film remaining rate and patterning characteristics.

[0195] [ka]

[0196] In formula (b1-II-3), R 13 , R 14 , R 15 , R 16 , m and n are the same as those in formula (b1-II), and R Z represents a hydrogen atom or a polybasic acid residue.

[0197] 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 (b1-II-3) may be linked via the following. 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. Among these, 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.

[0198] (b1-II) The partial structure represented by the formula (b1-II-3) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types, and examples thereof include R Z is a hydrogen atom, and R Z However, polybasic acid residues may be present in the mixture.

[0199] Furthermore, the number of partial structures represented by the formula (b1-II) contained in one molecule of the epoxy (meth)acrylate resin (b1-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. For example, 1 to 20 is preferred, more preferably 1 to 15, and even more preferably 3 to 10. By ensuring that the number is equal to or greater than the lower limit, a strong film tends to be obtained and surface roughness tends to be less likely to occur. By ensuring that the number is equal to or less than the upper limit, deterioration in sensitivity and film loss tend to be easily suppressed, and resolution tends to be improved.

[0200] The weight-average molecular weight (Mw) of the (b1-II) epoxy (meth)acrylate resin, measured by gel permeation chromatography (GPC) in terms of polystyrene, is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, more preferably 20,000 or less, even more preferably 10,000 or less, even more preferably 7,000 or less, and particularly preferably 5,000 or less. For example, it is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, even more preferably 1,000 to 10,000, even more preferably 2,000 to 7,000, and particularly preferably 2,000 to 5,000. By setting it to be equal to or greater than the lower limit, patterning properties tend to be improved. By setting it to be equal to or less than the upper limit, a strong film tends to be obtained and surface roughness tends to be less likely to occur.

[0201] The acid value of the (b1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, even more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, particularly preferably 80 mgKOH / g or more, and most preferably 100 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less. For example, 10 mgKOH / g to 200 mgKOH / g is preferred, 20 mgKOH / g to 200 mgKOH / g is more preferred, 40 mgKOH / g to 150 mgKOH / g is even more preferred, 60 mgKOH / g to 150 mgKOH / g is even more preferred, 80 mgKOH / g to 120 gKOH / g is particularly preferred, and 100 mgKOH / g to 120 gKOH / g is particularly preferred. By setting the concentration at or above the lower limit, a strong film tends to be easily obtained. By setting the concentration at or below the upper limit, the development solubility tends to be improved, and the resolution tends to be good.

[0202] The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more resins. Furthermore, 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.

[0203] Furthermore, from the viewpoint of compatibility with pigments, dispersants, etc., it is preferable to use (b2) an acrylic copolymer resin as (b) the alkali-soluble resin, and those described in JP 2014-137466 A can be preferably used.

[0204] Examples of acrylic copolymer resins include copolymers of an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as "unsaturated monomer (b2-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2-2)"). Examples of the unsaturated monomer (b2-1) 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 (b2-1) can be used alone or in combination of two or more.

[0205] Examples of the unsaturated monomer (b2-2) 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;

[0206] 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;

[0207] 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 (b2-2) can be used alone or in combination of two or more.

[0208] In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By copolymerizing the unsaturated monomer (b2-1) in such a range, it tends to be possible to obtain a photosensitive coloring composition excellent in alkali developability and storage stability.

[0209] Examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) 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. The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) 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.

[0210] In addition, resins described in WO 2016 / 194619 and WO 2017 / 154439 may also be used.

[0211] <(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.

[0212] Examples of the metallocene compound include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyltitanium Examples of the titanium bis(2,6-difluorophenyl-1-yl) include titanium dioxide (2,6-difluoro-3-(pyrro-1-yl)-phenyl-1-yl), ...

[0213] 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.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] As the 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. Since the 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, and it is possible to obtain a highly sensitive photosensitive coloring composition with a small amount.

[0218] Examples of the oxime ester compounds include compounds represented by the following general formula (IV).

[0219] [ka]

[0220] In the above 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.

[0221] R 21a In the formula, the number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in a solvent 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. For example, specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group. Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, or an N-acetyl-N-acetoxyamino group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0222] 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 coloring 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.

[0223] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, 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. Among these, from the viewpoint of developability, R 21ais preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group which has a linked alkoxy group as a substituent.

[0224] Also, R 21b Examples 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.

[0225] Also, R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but from the viewpoint of solubility in a solvent 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 of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group. Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group, and from the viewpoint of ease of synthesis, it is preferable that the alkanoyl group is unsubstituted.

[0226] Also, R 22a Although the number of carbon atoms in the aryloyl group is not particularly limited, from the viewpoints of solubility in a solvent 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 of the aryloyl group 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, and from the viewpoint of ease of synthesis, it is preferable that the aryloyl group is unsubstituted. Among these, from the viewpoint of sensitivity, 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.

[0227] The initiators described in JP 2016-133574 A are also preferably used because they reduce contamination of the liquid crystal layer by colorants.

[0228] 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.

[0229] Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Examples 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.

[0230] 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.

[0231] <(d) Ethylenically unsaturated compounds> The photosensitive coloring 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, and specific examples thereof include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters of polyhydric or monohydric alcohols.

[0232] 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. For example, 2 to 8 is preferred, 2 to 7 is more preferred, 4 to 7 is even more preferred, and 5 to 7 is 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 solvents tends to be improved. 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.

[0233] 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 cronate is replaced with cronate; and maleic acid esters in which maleate is replaced with maleate.

[0234] 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.

[0235] 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.

[0236] Other useful polyfunctional ethylenic monomers for use in the present invention include, for example, 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 hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

[0237] 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 Nippon Synthetic Chemical Industry Co., Ltd.).

[0238] Among these, 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.

[0239] <(e) Solvent> The photosensitive coloring composition of the present invention contains (e) a solvent. By containing (e) a solvent, (a) the colorant can be dispersed or dissolved in the solvent, and application becomes easy. The photosensitive coloring composition of the present invention is usually used in a state in which (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, (d) ethylenically unsaturated compound, (f) dispersant, and other various materials used as needed are dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coating properties.

[0240] 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.

[0241] 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; 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;

[0242] 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; 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;

[0243] 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; 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;

[0244] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; 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;

[0245] Examples of commercially available organic solvents that can be used 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.

[0246] When colored spacers are formed by photolithography, it is preferable to select an organic solvent having a boiling point of 100 to 200°C, more preferably 120 to 170°C.

[0247] Of the above organic solvents, 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. 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 in terms of the solubility of the components in the composition. Glycol monoalkyl ethers have high polarity, and if added in excessive amounts, the pigment tends to aggregate, resulting in a decrease in storage stability, such as an increase in the viscosity of the photosensitive coloring composition obtained later. 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.

[0248] It is also preferable to use an organic solvent having a boiling point of 150°C or higher (hereinafter sometimes referred to as a "high boiling point solvent"). By using such a high boiling point solvent in combination, the photosensitive coloring composition becomes less likely 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 the colorant, for example, at the tip of the 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.

[0249] 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.

[0250] 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. Among the various solvents mentioned above, 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.

[0251] <(f) Dispersant> The photosensitive coloring composition of the present invention contains (f) a dispersant, which allows the (a) colorant to be stably dispersed. The dispersant (f) in the photosensitive coloring composition of the present invention contains a dispersant (f1) (hereinafter sometimes referred to as "dispersant (f1)") having a repeating unit represented by the following general formula (1):

[0252] [ka]

[0253] (In formula (1), R 1 ~R 3 are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 ~R 3Two or more of these may be bonded to each other to form a ring structure. R 4 is a hydrogen atom or a methyl group. X is a divalent linking group. Y - is a counter anion represented by the following general formula (2):

[0254] [ka]

[0255] (In formula (2), R 5 represents an alkyl group which may have a substituent.

[0256] Dispersant (f1) is a dispersant with an ammonium group and a counter anion of an alkylsulfonate ion. The alkylsulfonate ion is stably bonded to the ammonium group as an anion derived from an ester. Therefore, even when immersed in an amine solvent such as N-methylpyrrolidone (NMP), the dispersant is stable and does not easily separate from the colorant. It is believed that the dispersant remains adsorbed and coated on the surface of the colorant, reducing the likelihood of the colorant leaching out as an impurity.

[0257] On the other hand, the counter anion in general formula (2) is stably bonded to the ammonium group as a sulfonate ion derived from an ester, so even if excess dispersant that is not adsorbed to the pigment remains in the cured product, it is unlikely to be liberated into the liquid crystal as a sulfonate ion, and therefore is unlikely to affect the alignment of the liquid crystal, which is thought to make the voltage holding ratio less likely to decrease.It is particularly unlikely to be liberated even after UV irradiation, and it is presumed that the voltage holding ratio is less likely to decrease.

[0258] (R 1 ~R 3 ) In the formula (1), R 1 ~R 3 are each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent. R1 ~R 3 The alkyl group in may be a straight-chain, branched-chain or cyclic alkyl group, and is preferably a straight-chain alkyl group from the viewpoint of voltage holding ratio after UV irradiation and NMP resistance. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 6 or less, even more preferably 2 or less, and usually 1 or more. By making the number of carbon atoms equal to or less than the upper limit, the stability of the dispersion over time tends to be improved. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. From the viewpoint of the stability of the dispersion over time, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. Examples of the substituent that the alkyl group may have include alkoxy groups such as a methoxy group and an ethoxy group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; aralkyl groups such as a benzyl group and a phenethyl group; and aryl groups such as a phenyl group and a naphthyl group. From the viewpoint of dispersibility, the alkyl group is preferably unsubstituted.

[0259] R 1 ~R 3 The aryl group in the formula (I) includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 24 or less, more preferably 18 or less, even more preferably 12 or less, and usually at least 6. By making it equal to or less than the upper limit, dispersibility tends to be improved. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. From the viewpoint of dispersibility, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred. Examples of the substituent that the aryl group may have include alkyl groups such as a methyl group and an ethyl group; alkoxy groups such as a methoxy group and an ethoxy group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; and aralkyl groups such as a benzyl group and a phenethyl group. From the viewpoint of dispersibility, the aryl group is preferably unsubstituted.

[0260] In the formula (1), R 1 ~R 3Two or more of these may be bonded to each other to form a cyclic structure, and examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. Specific examples include the following.

[0261] [ka]

[0262] (In the above formula, R is R 1 ~R 3 These cyclic structures may further have a substituent. * represents a bond.)

[0263] Among these, R 1 ~R 3 are each independently preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0264] (X) In the formula (1), X is a divalent linking group. Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 6 -group, -COOR 7 -group (wherein R 6 and R 7 are each independently 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 from the viewpoint of dispersibility, -COOR 7 - group is preferred. 7 Among these, from the viewpoint of the stability over time of the dispersion, alkylene groups having 1 to 10 carbon atoms are preferred, alkylene groups having 1 to 5 carbon atoms are more preferred, and alkylene groups having 1 to 3 carbon atoms are even more preferred.

[0265] (Y - ) In the formula (1), Y - is a counter anion represented by the following general formula (2).

[0266] [ka]

[0267] (In formula (2), R 5 represents an alkyl group which may have a substituent.

[0268] (R 5 ) R 5 The alkyl group in may be a straight-chain, branched-chain or cyclic alkyl group, and is preferably a straight-chain alkyl group from the viewpoint of voltage holding ratio after ultraviolet irradiation. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 6 or less, more preferably 4 or less, even more preferably 2 or less, and usually 1 or more. By setting the number of carbon atoms to the upper limit or less, the voltage holding ratio after ultraviolet irradiation tends to be high. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. From the viewpoint of the voltage holding ratio after ultraviolet irradiation, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. Examples of the substituent that the alkyl group may have include alkoxy groups such as a methoxy group and an ethoxy group; and halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of the voltage holding ratio after ultraviolet light irradiation, the alkyl group is preferably unsubstituted. Among these, R 5 is preferably an unsubstituted alkyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0269] The dispersant (f1) has a repeating unit represented by the general formula (1) above, but may also have other repeating units. From the viewpoint of the voltage holding ratio before and after ultraviolet irradiation, the dispersant (f1) preferably has a repeating unit represented by the following general formula (3).

[0270] [ka]

[0271] (In formula (3), R 8 and R 9 R is independently an alkyl group which may have a substituent, or an aryl group which may have a substituent. 8 and R 9 may be bonded to each other to form a ring structure. R 10 is a hydrogen atom or a methyl group. Z is a divalent linking group.

[0272] In the formula (3), R 8 and R 9 are each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent. The alkyl group which may have a substituent and the aryl group which may have a substituent are R 1 ~R 3 The above-mentioned compounds can be preferably used.

[0273] In the formula (3), R 8 and R 9 may be bonded to each other to form a cyclic structure. Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. Specific examples include the following:

[0274] [ka]

[0275] (These cyclic structures may further have a substituent. * represents a bond.)

[0276] In the formula (3), Z is a divalent linking group. As the divalent linking group, those exemplified as X in the formula (1) can be preferably used.

[0277] Furthermore, the dispersant (f1) preferably has a repeating unit represented by the following general formula (4), from the viewpoint of increasing compatibility with solvents and alkali-soluble resins and improving dispersion stability.

[0278] [ka]

[0279] (In formula (4), R 11 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R 12 is a hydrogen atom or a methyl group.

[0280] (R 11 ) R 11 The alkyl group in may be a linear, branched, or cyclic alkyl group. From the viewpoint of compatibility with solvents and alkali-soluble resins, a linear alkyl group is preferred, and from the viewpoint of affinity with pigments, a branched alkyl group is preferred. The number of carbon atoms in the alkyl group 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, and even more preferably 6 or less. By making the number of carbon atoms equal to or greater than the lower limit, affinity for the pigment tends to be enhanced. By making the number of carbon atoms equal to or less than the upper limit, compatibility with solvents and alkali-soluble resins tends to be enhanced, improving dispersibility. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an ethylhexyl group. From the viewpoint of compatibility with solvents and alkali-soluble resins, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. Examples of the substituent that the alkyl group may have include alkoxy groups such as a methoxy group or an ethoxy group; halogen atoms such as a fluorine atom, a chlorine atom or a bromine atom; and aryl groups such as a phenyl group or a naphthyl group. From the viewpoint of compatibility with solvents and alkali-soluble resins, the alkyl group is preferably unsubstituted, and from the viewpoint of affinity with pigments, the alkyl group is preferably a phenyl group.

[0281] R 11 The aryl group in the formula (I) includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is usually 6 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. By setting the number of carbon atoms below the upper limit, affinity for the pigment tends to be enhanced. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. From the viewpoint of dispersibility, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. Examples of the substituent that the aryl group may have include alkyl groups such as a methyl group and an ethyl group; alkoxy groups such as a methoxy group and an ethoxy group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; aryl groups such as a phenyl group and a naphthyl group; and aralkyl groups such as a benzyl group and a phenethyl group. From the viewpoint of dispersibility, the aryl group is preferably unsubstituted.

[0282] Among these, R 11 As the alkyl group, an alkyl group which may have a substituent is preferable, an unsubstituted alkyl group is more preferable, and a methyl group, a butyl group, or an ethylhexyl group is even more preferable.

[0283] From the viewpoint of compatibility with solvents and alkali-soluble resins, the dispersant (f1) preferably has a repeating unit represented by the following general formula (5).

[0284] [ka]

[0285] (In formula (5), R 13 is a methylene group, an ethylene group, or a propylene group. R 14 is a methyl group, an ethyl group, or a propyl group. R 15 is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

[0286] R 13 is a methylene group, an ethylene group, or a propylene group, but is preferably an ethylene group from the viewpoint of compatibility with solvents and alkali-soluble resins. R 14 is a methyl group, an ethyl group, or a propyl group, and from the viewpoint of compatibility with solvents and alkali-soluble resins, a methyl group or an ethyl group is preferred, and an ethyl group is more preferred.

[0287] n is an integer of 1 to 20, preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less. For example, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 5 is even more preferred. By adjusting the content to be equal to or greater than the lower limit, compatibility with solvents and alkali-soluble resins tends to improve, whereas by adjusting the content to be equal to or less than the upper limit, affinity with pigments tends to be increased, improving dispersibility.

[0288] The content of the repeating unit represented by the general formula (1) (hereinafter sometimes referred to as "repeating unit (1)") in dispersant (f1) is not particularly limited, but is preferably 2 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, even more preferably 10 mol% or more, and particularly preferably 12 mol% or more, and is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. For example, 2 mol% to 50 mol% is preferred, more preferably 5 mol% to 40 mol%, more preferably 7 mol% to 30 mol%, even more preferably 7 mol% to 20 mol%, and particularly preferably 7 mol% to 15 mol%. By ensuring that the content is equal to or greater than the lower limit, the stability of the dispersion over time tends to be improved, and by ensuring that the content is equal to or less than the upper limit, the dispersibility tends to be improved.

[0289] When the dispersant (f1) contains a repeating unit represented by the general formula (3) (hereinafter, sometimes referred to as "repeating unit (3)"), its content is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 12 mol% or more, and particularly preferably 15 mol% or more, based on the total repeating units. It is also preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. For example, it is preferably 5 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, even more preferably 12 mol% to 30 mol%, and particularly preferably 15 mol% to 20 mol%. By setting it to the lower limit or more, the dispersibility tends to be good. By setting it to the upper limit or less, the stability of the dispersion over time tends to be good.

[0290] When the dispersant (f1) contains a repeating unit (3), the content of the repeating unit (1) relative to the total of the repeating units (1) and (3) is typically 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, and particularly preferably 30 mol% or more. It is typically 100 mol% or less, preferably 80 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. For example, it is preferably 5 mol% to 100 mol%, more preferably 10 mol% to 80 mol%, more preferably 20 mol% to 60 mol%, even more preferably 25 mol% to 50 mol%, and particularly preferably 30 mol% to 40 mol%. By setting the content at or above the lower limit, the voltage holding ratio after UV irradiation and NMP resistance tend to be improved. By setting the content at or below the upper limit, the temporal stability of the dispersion tends to be improved.

[0291] When the dispersant (f1) contains a repeating unit represented by the general formula (4) (hereinafter, sometimes referred to as "repeating unit (4)"), its content is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, and particularly preferably 60 mol% or more, and is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 65 mol% or less. For example, 20 mol% to 90 mol% is preferred, more preferably 30 mol% to 90 mol%, more preferably 40 mol% to 80 mol%, even more preferably 50 mol% to 80 mol%, and particularly preferably 60 mol% to 80 mol%. By setting the content at or above the lower limit, affinity for the pigment tends to be enhanced. By setting the content at or below the upper limit, compatibility with solvents and alkali-soluble resins tends to be enhanced.

[0292] When the dispersant (f1) contains a repeating unit represented by the general formula (5) (hereinafter, sometimes referred to as "repeating unit (5)"), its content is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, based on the total repeating units. For example, it is preferably 1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, more preferably 2 mol% to 15 mol%, even more preferably 2 mol% to 10 mol%, and particularly preferably 3 mol% to 5 mol%. By setting the content at or above the lower limit, compatibility with solvents and alkali-soluble resins tends to be improved. By setting the content at or below the upper limit, affinity for the pigment tends to be improved.

[0293] When the dispersant (f1) has the repeating unit (1) and the repeating unit (3), from the viewpoint of dispersibility, it is preferably a block copolymer having a B block having the repeating unit (1) and the repeating unit (3) and an A block not having the repeating unit (1) and the repeating unit (3). The block copolymer is preferably an AB block copolymer or an ABA block copolymer.

[0294] In the B block, the repeating unit (1) and the repeating unit (3) may be contained in either a random copolymerization or a block copolymerization form. Furthermore, two or more types of each of the repeating unit (1) and the repeating unit (3) may be contained in the B block, and in this case, each repeating unit may be contained in the B block in either a random copolymerization or a block copolymerization form.

[0295] When the dispersant (f1) has the repeating unit (4) or the repeating unit (5), they may be contained in the A block, and may be contained in either a random copolymerization or a block copolymerization form. Furthermore, two or more types of each of the repeating units (4) and (5) may be contained in the A block, and in that case, each repeating unit may be contained in the A block in either a random copolymerization or a block copolymerization form.

[0296] The A block may contain repeating units other than the repeating units (4) and (5). Examples of such repeating units include repeating units derived from 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.

[0297] The amine value of the dispersant (f1) 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, particularly preferably 45 mgKOH / g or more, and is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, even more preferably 80 mgKOH / g or less, and particularly preferably 60 mgKOH / g or less. For example, 20 mgKOH / g to 150 mgKOH / g is preferred, more preferably 30 mgKOH / g to 100 mgKOH / g, even more preferably 40 mgKOH / g to 80 mgKOH / g, and particularly preferably 45 mgKOH / g to 60 mgKOH / g. By setting the amine value at or above the lower limit, dispersibility tends to be improved. By setting the amine value at or below the upper limit, the stability of the dispersion over time tends to be improved. The amine value is expressed as the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant (f1).

[0298] The acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, even more preferably 1 mgKOH / g, and particularly preferably 0 mgKOH / g.

[0299] The weight-average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less. For example, it is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 7,000 to 10,000. By setting it to the lower limit or more, dispersibility tends to improve. By setting it to the upper limit or less, the stability over time of the dispersion tends to improve. In the dispersant of the present invention, the additional anion Y - The presence of Y may prevent the weight average molecular weight from being measured satisfactorily. - The theoretical molecular weight calculated from the weight average molecular weight before addition may be used. The theoretical molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less. For example, it is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 7,000 to 10,000. By setting it to the lower limit or more, dispersibility tends to improve. By setting it to the upper limit or less, the stability over time of the dispersion tends to improve.

[0300] The method for producing the dispersant (f1) is not particularly limited, and any known method can be used. For example, the dispersant (f1) can be produced by reacting a precursor of the dispersant (f1) containing the repeating unit (3) with a compound represented by the following general formula (2'):

[0301] [ka]

[0302] (In formula (2'), R 5 is the same as in formula (2). 50 is R in the formula (1). 1 ~R 3 is equivalent to either

[0303] The dispersant (f) in the photosensitive coloring composition of the present invention may contain a dispersant other than the dispersant (f1) (hereinafter, sometimes referred to as "other dispersants").

[0304] As the other dispersants, from the viewpoint of dispersion stability, dispersants having, as a functional group, for example, a carboxy 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 are preferred. Among them, dispersants having a basic functional group, for example, 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 are more preferred. Furthermore, polymer dispersants are preferred from the viewpoint that the pigment can be dispersed with a small amount of dispersant.

[0305] Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of a monomer having an amino group and a macromonomer, 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.

[0306] Examples of such polymer 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.).

[0307] Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK 160 to 166, 182 series (all urethane-based), DISPERBYK 2000, 2001, BYK-LPN21116 (all acrylic-based) (all manufactured by BYK-Chemie).

[0308] The other dispersants may be used alone or in combination of two or more.

[0309] <Other ingredients of the photosensitive coloring composition> In addition to the above-mentioned components, the photosensitive coloring 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.

[0310] (1) Adhesion improver The photosensitive coloring composition of the present invention may contain an adhesion improver to improve adhesion to the substrate. Preferred adhesion improvers are 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.

[0311] 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. 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.

[0312] [ka]

[0313] In the above general formulae (g1), (g2) and (g3), R 51 represents 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.

[0314] (2) Surfactants The photosensitive coloring composition of the present invention may contain a surfactant to improve the coating properties.

[0315] As the surfactant, various types of surfactants can be used, such as anionic, cationic, nonionic, amphoteric surfactants, etc. Among them, nonionic surfactants are preferred 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 such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu 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.

[0316] (3) Pigment derivatives The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability. 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. Furthermore, a single pigment skeleton may contain multiple such substituents.

[0317] 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.

[0318] (4) Photoacid generator A photoacid generator is a compound that can generate an acid by ultraviolet light, and the action of the acid generated upon exposure to light promotes a crosslinking reaction in the presence of a crosslinking agent such as a melamine compound. Among photoacid generators, those that have high solubility in solvents, particularly in solvents used in photosensitive coloring compositions, are preferred. Examples of such compounds include diaryliodonium compounds such as diphenyliodonium, ditolyliodonium, phenyl(p-anisyl)iodonium, bis(m-nitrophenyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p-chlorophenyl)iodonium, bis(n-dodecyl)iodonium, p-isobutylphenyl(p-tolyl)iodonium, and p-isopropylphenyl(p-tolyl)iodonium; chlorides, bromides, or boron fluorides, hexafluorophosphate salts, hexafluoroarsenate salts, aromatic sulfonates, and tetrakis(pentafluorophenyl)borate salts of triarylsulfonium compounds such as triphenylsulfonium; sulfonium organoboron complexes such as diphenylphenacylsulfonium(n-butyl)triphenylborate; and triazine compounds such as 2-methyl-4,6-bistrichloromethyltriazine and 2-(4-methoxyphenyl)-4,6-bistrichloromethyltriazine.

[0319] (5) Crosslinking agent The photosensitive coloring composition of the present invention may further contain a crosslinking agent, such as a melamine or guanamine compound, such as the melamine or guanamine compound represented by the following general formula (6):

[0320] [ka]

[0321] In formula (6), R 61 Ha-NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms, and R 61 Ga-NR 66 R 67R for groups 62 , R 63 , R 64 , R 65 , R 66 and R 67 One of them is -CH2OR 68 represents a group, and R 61 When R is an aryl group having 6 to 12 carbon atoms, 62 , R 63 , R 64 and R 65 One of them is -CH2OR 68 represents a group, and R 62 , R 63 , R 64 , R 65 , R 66 and R 67 the remainder are independently hydrogen or -CHOR 68 represents a group, and R 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and these phenyl groups and naphthyl groups may be substituted with a substituent such as an alkyl group, an alkoxy group, or a halogen atom. The number of carbon atoms in the alkyl group and the alkoxy group is each 1 to 6. R 68 The alkyl group represented by the formula (I) is preferably a methyl group or an ethyl group, more preferably a methyl group.

[0322] Melamine compounds corresponding to general formula (6), i.e., compounds of the following general formula (6-1), include, for example, hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, and hexaethoxymethylmelamine.

[0323] [ka]

[0324] In formula (6-1), R 62 , R 63 , R 64 , R 65, R 66 and R 67 If one of the groups is an aryl group, R 62 , R 63 , R 64 and R 65 One of them is -CH2OR 68 represents a group, and R 62 , R 63 , R 64 , R 65 , R 66 and R 67 the remainder are independently a hydrogen atom or -CHOR 68 represents a group, and R 68 represents a hydrogen atom or an alkyl group.

[0325] Guanamine compounds corresponding to general formula (6), i.e., R 61 Compounds in which is aryl include, for example, tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, and tetraethoxymethylbenzoguanamine.

[0326] Crosslinking agents having a methylol group or a methylol alkyl ether group can also be used, such as 2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl)perhydro-1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethyleneurea or its dimethyl ether, 3,5-bis(hydroxymethyl)perhydro-1,3,5-oxadiazin-4-one (commonly known as dimethyloluron) or its dimethyl ether, and tetramethylolglyoxal diurein or its tetramethyl ether.

[0327] These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably 0.1 to 15 mass % of the total solid content of the photosensitive coloring composition, and particularly preferably 0.5 to 10 mass %.

[0328] (6) Mercapto compounds A mercapto compound can also be added as a polymerization accelerator and to improve adhesion to the substrate.

[0329] 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( Examples of suitable mercapto compounds include mercapto compounds having a heterocycle, such as 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, butanediol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. These compounds may be used singly or in combination of two or more.

[0330] (7) Polymerization inhibitor The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. By containing a polymerization inhibitor, it is thought that the radical polymerization of the lower layer of the coating film is inhibited, and therefore the taper angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled. 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. (b) When producing an alkali-soluble resin, 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 in the resin, a polymerization inhibitor identical to or different from the polymerization inhibitor may be added when producing the photosensitive coloring composition.

[0331] When the photosensitive coloring 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 coloring composition. 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 it to the lower limit or higher, the shape of the cured product tends to be more controllable. By setting it to the upper limit or lower, the required sensitivity tends to be maintained.

[0332] <Content ratio of each component in the photosensitive coloring composition> The content of the (a) colorant in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 35% by mass or more, based on the total solid content. It is also preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less. For example, it is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, even more preferably 20% by mass to 60% by mass, even more preferably 20% by mass to 50% by mass, and particularly preferably 20% by mass to 45% by mass. By setting it to the lower limit or more, light-blocking properties tend to be ensured. By setting it to the upper limit or less, patterning properties tend to be improved.

[0333] When the photosensitive coloring composition contains an organic coloring pigment, its content is not particularly limited, but is preferably 5% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 35% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less, based on the total solid content of the photosensitive coloring composition. For example, 5% by mass to 70% by mass is preferred, more preferably 20% by mass to 70% by mass, even more preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass. By setting the content at or above the lower limit, light-blocking properties tend to be improved while suppressing loss of UV light required for curing. By setting the content at or below the upper limit, NMP resistance tends to be improved.

[0334] 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, and particularly preferably 12% by mass or more in the (a) colorant. It is also preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. For example, it is preferably 5% by mass to 40% by mass, more preferably 8% by mass to 40% by mass, even more preferably 10% by mass to 30% by mass, and particularly preferably 12% by mass to 20% 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 result in high sensitivity.

[0335] When the (a) colorant contains a blue pigment and / or a purple pigment, the total content of the blue pigment and the purple 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, particularly preferably 80% by mass or more, and is preferably 95% by mass or less, more preferably 92% by mass or less, and particularly preferably 90% by mass or less. For example, 30% by mass to 95% by mass is preferred, more preferably 50% by mass to 95% by mass, more preferably 70% by mass to 92% by mass, and particularly preferably 80% by mass to 90% by mass. By setting the content at or above the lower limit, the light-blocking properties tend to be improved. By setting the content at or below the upper limit, the NMP resistance tends to be improved.

[0336] When the photosensitive coloring composition contains a black pigment, its content is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, even 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, for example, 2% by mass to 60% by mass is preferred, more preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass. By setting it to the lower limit or more, light-shielding properties tend to be improved. By setting it to the upper limit or less, NMP resistance tends to be improved.

[0337] Furthermore, when the photosensitive coloring composition contains an organic black pigment, its content is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, even 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, for example, 2% by mass to 60% by mass is preferred, more preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass. By setting it to the lower limit or more, light-shielding properties tend to be improved. By setting it to the upper limit or less, NMP resistance tends to be improved.

[0338] When the (a) colorant contains an organic black 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 in the (a) colorant. It is also preferably 100% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. For example, it is preferably 5% by mass to 100% by mass, more preferably 10% by mass to 100% by mass, more preferably 15% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass. By setting it to the lower limit or more, light-blocking properties tend to be improved. By setting it to the upper limit or less, NMP resistance tends to be improved.

[0339] Furthermore, when the photosensitive coloring composition contains carbon black as an inorganic black pigment, its content is not particularly limited, but is preferably 5% by mass or more in the (a) colorant, more preferably 10% by mass or more, even more preferably 15% 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. For example, 5% by mass to 60% by mass is preferred, more preferably 10% by mass to 50% by mass, and even more preferably 15% by mass to 40% by mass is preferred. By setting it to the lower limit or more, light-blocking properties tend to be improved. By setting it to the upper limit or less, NMP resistance tends to be improved.

[0340] Furthermore, when the (a) colorant contains an organic color pigment and a black pigment, the total content ratio thereof 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 is preferably 100% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less in the (a) colorant. For example, 5% by mass to 100% by mass is preferred, more preferably 10% by mass to 70% by mass, and even more preferably 15% by mass to 50% by mass is preferred. By setting the content at or above the lower limit, light-blocking properties tend to be improved. By setting the content at or below the upper limit, NMP resistance tends to be improved.

[0341] The content of (b) alkali-soluble resin is not particularly limited, but is usually 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 35% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. It is usually 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, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less. For example, 5% by mass to 85% by mass is preferred, 5% by mass to 80% by mass is more preferred, 10% by mass to 70% by mass is even more preferred, 20% by mass to 60% by mass is even more preferred, 30% by mass to 50% by mass is particularly preferred, and 35% by mass to 45% by mass is particularly preferred. By setting it at or above the lower limit, it is possible to suppress a decrease in the solubility of the unexposed portion in the developer, and to suppress development defects. By setting the content to the upper limit or less, it is possible to maintain appropriate sensitivity, to prevent the exposed area from being dissolved by a developer, and to prevent deterioration in the sharpness and adhesion of the pattern.

[0342] The content of the (b1) epoxy (meth)acrylate resin is not particularly limited, but is typically 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total solids content of the photosensitive coloring composition of the present invention. It is typically 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less. For example, 5% to 50% by mass is preferred, 10% to 50% by mass is more preferred, 15% to 40% by mass is even more preferred, and 20% to 30% by mass is particularly preferred. By setting the content at or above the lower limit, the solubility of the unexposed portion in the developer tends to be ensured. By setting the content at or below the upper limit, the appropriate sensitivity can be maintained, dissolution of the exposed portion in the developer can be suppressed, and a decrease in the sharpness and adhesion of the pattern can be suppressed.

[0343] The content of the (b1) epoxy (meth)acrylate resin in the (b) alkali-soluble resin is not particularly limited, but is typically 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more, and typically 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less. For example, 20% by mass to 90% by mass is preferred, 30% by mass to 85% by mass is more preferred, and 40% by mass to 80% by mass is even more preferred. By setting the content at or above the lower limit, the solubility of the unexposed portion in the developer tends to be ensured. By setting the content at or below the upper limit, the appropriate sensitivity can be maintained, dissolution of the exposed portion in the developer can be suppressed, and a decrease in the sharpness and adhesion of the pattern can be suppressed.

[0344] The content of (c) the photopolymerization initiator is not particularly limited, but is usually 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, based on the total solid content of the photosensitive coloring composition of the present invention. It is usually 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. For example, 0.1% by mass to 15% by mass is preferred, 0.5% by mass to 15% by mass is more preferred, 1% by mass to 10% by mass is even more preferred, 2% by mass to 8% by mass is even more preferred, and 3% by mass 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 the unexposed portion in the developer solution tends to be suppressed, and development defects tend to be suppressed.

[0345] 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 solid content of the photosensitive coloring composition of the present invention. 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, per 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. In addition, when a sensitizing dye is used together with the (c) photopolymerization initiator, the content ratio is not particularly limited, but from the viewpoint of sensitivity, it is usually 20 mass % or less, preferably 15 mass % or less, more preferably 10 mass % or less of the total solid content in the photosensitive coloring composition.

[0346] The content of the (d) ethylenically unsaturated compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. For example, 1% by mass to 30% by mass is preferred, 5% by mass to 20% by mass is more preferred, and 10% by mass to 15% by mass is even more preferred. By setting the content at or above the lower limit, appropriate sensitivity can be maintained, dissolution of exposed areas by the developer can be suppressed, and deterioration of pattern sharpness and adhesion can be suppressed. By setting the content at or below the upper limit, increased penetration of the developer into exposed areas can be suppressed, making it easier to obtain a good image.

[0347] The photosensitive coloring composition of the present invention is prepared by using the (e) solvent so that the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less. For example, the composition is prepared so that the total solid content is 5% by mass to 50% by mass, preferably 10% by mass to 30% by mass, more preferably 15% by mass to 25% by mass.

[0348] The content of (f) dispersant is not particularly limited, but is typically 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and typically 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total solid content of the photosensitive coloring composition. For example, 1% to 30% by mass is preferred, 1% to 20% by mass is more preferred, 3% to 15% by mass is even more preferred, and 5% to 10% 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, the proportions of other components can be maintained at a constant level relative to one another, which tends to prevent deterioration in sensitivity, plate-making properties, etc.

[0349] The content of the dispersant (f1) is not particularly limited, but is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total solid content of the photosensitive coloring composition. For example, 1% by mass to 30% by mass is preferred, more preferably 1% by mass to 20% by mass, even more preferably 3% by mass to 15% by mass, and particularly preferably 5% by mass to 10% by mass. By setting the content at or above the lower limit, dispersibility tends to be improved. By setting the content at or below the upper limit, the voltage holding ratio after ultraviolet irradiation tends to be higher.

[0350] The content of the dispersant (f1) is not particularly limited, but is usually 10% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, in the dispersant (f), and is usually 100% by mass or less. By making it equal to or more than the lower limit, NMP resistance tends to improve.

[0351] Furthermore, the content ratio of the dispersant (f) relative to 100 parts by mass of the colorant (a) 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 usually 50 parts by mass or less, particularly preferably 30 parts by mass or less. For example, 5 to 50 parts by mass is preferred, more preferably 10 to 50 parts by mass, and even more preferably 15 to 30 parts by mass. 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, the proportions of other components are relatively reduced, which tends to prevent deterioration in sensitivity, plate-making properties, etc.

[0352] On the other hand, the content ratio of (b) alkali-soluble resin per 100 parts by mass of (d) ethylenically unsaturated compound is usually 80 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 250 parts by mass or more, and is usually 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. For example, 80 parts by mass to 700 parts by mass is preferred, more preferably 100 parts by mass to 700 parts by mass, more preferably 150 parts by mass to 500 parts by mass, even more preferably 200 parts by mass to 400 parts by mass, and particularly preferably 250 parts by mass to 300 parts by mass. By setting the content at or above the lower limit, an appropriate dissolution and development state without peeling or the like tends to be achieved. By setting the content at or below the upper limit, an appropriate dissolution time in the developer tends to be obtained.

[0353] 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 % of the total solid content of the photosensitive coloring composition. By setting it to the lower limit or more, it tends to be possible to sufficiently obtain the effect of improving adhesion. By setting it to the upper limit or less, it tends to be possible to suppress a decrease in sensitivity and defects caused by residue remaining after development.

[0354] 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 % of the total solid content of the photosensitive coloring composition. By setting the content at or above the lower limit, smoothness and uniformity of the coating film tend to be easily achieved. By setting the content at or below the upper limit, smoothness and uniformity of the coating film tend to be easily achieved, and deterioration of other properties also tends to be suppressed.

[0355] <Physical Properties of Photosensitive Coloring Composition> The photosensitive coloring composition of the present invention has an optical density (OD) per 1 μm of film thickness of its coating film of 0.5 or more. It is more preferably 0.7 or more, even more preferably 1.0 or more, even more preferably 1.3 or more, and particularly preferably 1.5 or more. It is usually 4.0 or less, preferably 3.0 or less, and more preferably 2.0 or less. For example, it is preferably 0.5 to 4.0, more preferably 0.7 to 4.0, even more preferably 1.0 to 3.0, even more preferably 1.3 to 3.0, and particularly preferably 1.5 to 2.0. By setting it to the lower limit or more, sufficient light-blocking properties tend to be obtained. By setting it to the upper limit or less, the voltage holding ratio and NMP resistance tend to be good. The optical density (OD) per 1 μm of the coating film thickness can be measured using a coating film obtained by curing the photosensitive coloring composition of the present invention, and can be measured using a coating film that has been heat-cured at 230°C for 20 minutes. Optical density refers to the transmission optical density, which is the spectral sensitivity characteristic of the light receiving section, as indicated by the ISO visual density in the ISO 5-3 standard. The light source typically used is the A illuminant specified by the CIE (International Commission on Illumination). An example of a measuring instrument that can be used to measure transmission optical density is the X-Rite 361T(V) manufactured by Sakata Inx Engineering Corporation.

[0356] <Method for producing photosensitive coloring composition> The photosensitive coloring composition of the present invention is produced in accordance with a conventional method. Usually, it is preferable that the (a) colorant be 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 made into fine particles, thereby improving the coating properties of the resist.

[0357] The dispersion treatment is usually preferably carried out in a system using a combination of (a) a colorant, (e) a solvent, and (f) a dispersant, and 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 obtained pigment dispersion and photosensitive coloring composition from thickening over time, i.e., it has excellent dispersion stability. In this way, in the step of producing the photosensitive coloring 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 that can be used in the photosensitive coloring composition can be preferably used. In addition, as the content ratio of each colorant of the (a) colorant in the pigment dispersion, those that can be used in the photosensitive coloring composition can be preferably used.

[0358] When a dispersion treatment is carried out on a liquid containing all the components to be blended in the photosensitive coloring composition, the heat generated during the dispersion treatment may cause the highly reactive components to denature. Therefore, it is preferable to carry out 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 appropriate dispersion time varies depending on the liquid composition and the size of the dispersion treatment device, so it should be adjusted appropriately. A guideline for dispersion is to control the gloss of the pigment dispersion so that the 20° specular gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300. When the gloss of the photosensitive coloring 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. 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.

[0359] Next, the pigment dispersion obtained by the above-mentioned dispersion treatment and the other components contained in the photosensitive coloring composition are mixed to make a uniform solution or dispersion.In the manufacturing process of the photosensitive coloring composition, fine dust may be mixed in the liquid, so it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.

[0360] [Pigment dispersion for image display devices] The pigment dispersion for an image display device of the present invention contains (a) a colorant, (e) a solvent, and (f) a dispersant, and in particular, the (a) colorant contains a black pigment, and the (f) dispersant contains dispersant (f1). In the pigment dispersion for an image display device of the present invention, the (a) colorant, (e) solvent, and (f) dispersant can be preferably the same as those listed in the photosensitive coloring composition of the present invention. Similarly, in the pigment dispersion for an image display device of the present invention, the black pigment and dispersant (f1) can be preferably the same as those listed in the photosensitive coloring composition of the present invention.

[0361] In the pigment dispersion liquid for an image display device of the present invention, the content of the colorant (a) is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less, based on the total solid content. For example, 30% by mass to 80% by mass is preferred, more preferably 50% by mass to 75% by mass, and even more preferably 60% by mass to 70% by mass is preferred. By setting the content at or above the lower limit, the voltage holding ratio after UV irradiation and NMP resistance tend to be good. By setting the content at or below the upper limit, dispersibility tends to be good.

[0362] In the pigment dispersion for an image display device of the present invention, the content of the black pigment is not particularly limited, but is preferably 30% by mass or more of the total solids, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 80% by mass or more, and is preferably 75% by mass or less, more preferably 70% by mass or less. For example, 30% by mass to 80% by mass is preferred, more preferably 50% by mass to 75% by mass, and even more preferably 60% by mass to 70% by mass. By setting the content at or above the lower limit, the voltage holding ratio after UV irradiation and NMP resistance tend to be good. By setting the content at or below the upper limit, dispersibility tends to be good.

[0363] In the pigment dispersion for an image display device of the present invention, it is desirable to contain an organic black pigment represented by the above structural formula (1) among black pigments from the viewpoint of light-blocking properties when used as a photosensitive coloring composition. The content of the organic black pigment of structural formula (1) in the (a) colorant is preferably 10% by mass or more, more preferably 40% by mass or more, even more preferably 70% by mass or more, particularly preferably 90% by mass or more, and even particularly preferably 98% by mass or more, of the total (a) colorant.

[0364] In the pigment dispersion for an image display device of the present invention, the content of the dispersant (f) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more, based on the total solid content. It is also preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. For example, it is preferably 1% by mass to 35% by mass, more preferably 5% by mass to 30% by mass, even more preferably 8% by mass to 20% by mass, and particularly preferably 10% by mass to 15% by mass. Setting it to be equal to or greater than the lower limit tends to improve dispersibility. Setting it to be equal to or less than the upper limit tends to improve the voltage holding ratio after UV irradiation and NMP resistance.

[0365] In the pigment dispersion for an image display device of the present invention, the content of the dispersant (f1) 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, and is preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less, based on the total solids content. For example, 5% by mass to 35% by mass is preferred, more preferably 5% by mass to 30% by mass, even more preferably 8% by mass to 20% by mass, and particularly preferably 10% by mass to 15% by mass. By setting the content at or above the lower limit, dispersibility tends to be improved. By setting the content at or below the upper limit, the voltage holding ratio after UV irradiation and NMP resistance tend to be improved.

[0366] The content of the dispersant (f1) is not particularly limited, but is usually 10% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, in the dispersant (f), and is usually 100% by mass or less. By making it equal to or more than the lower limit, NMP resistance tends to improve.

[0367] The pigment dispersion for an image display device of the present invention is prepared by using the solvent (e) so that the total solid content is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and usually 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, preferably 10% by mass to 40% by mass, more preferably 15% by mass to 35% by mass, and even more preferably 20% by mass to 30% by mass.

[0368] [Cured product] The photosensitive coloring composition of the present invention can be cured to obtain the cured product of the present invention. The cured product of the present invention can be suitably used as a colored spacer. Furthermore, a cured product obtained by curing the photosensitive coloring composition of the present invention can be suitably used as a partition wall.

[0369] [Colored spacer] Next, the colored spacer using the photosensitive colored composition of the present invention will be described in accordance with its production method.

[0370] (1) Support The material of the support for forming the colored spacers is not particularly limited as long as it has adequate strength. Transparent substrates are mainly used, and examples of 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 resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass. Among these, glass and heat-resistant resins are preferred from the standpoint of heat resistance. In addition, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. In addition to transparent substrates, the substrate can also be formed on a TFT array.

[0371] If necessary, the support 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 transparent 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.

[0372] (2) Colored spacers The photosensitive coloring composition of the present invention is used for the same purpose as the known photosensitive coloring composition for color filter, but hereinafter, when used as color spacer (black photo spacer), the photosensitive coloring composition of the present invention is used to describe the specific example of the method for forming black photo spacer.

[0373] Typically, a photosensitive coloring composition is applied in the form of a film or pattern by coating or other methods onto a substrate on which a black photospacer is to be formed, and the solvent is dried. Subsequently, a pattern is formed by a method such as photolithography, which involves exposure and development. Thereafter, if necessary, additional exposure or heat curing treatment is performed to form a black photospacer on the substrate.

[0374] (3) Formation of colored spacers [1] Supply method to the board The photosensitive coloring 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. It may also 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.

[0375] The amount of coating varies depending on the application, but in the case of black photospacers, 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 spacers finally formed is uniform across the entire substrate. If the variation is small, unevenness defects that occur in liquid crystal panels can be suppressed.

[0376] When black photospacers having different heights are formed at once by photolithography using the photosensitive coloring composition of the present invention, the heights of the finally formed black photospacers will be different.

[0377] The substrate may be a known substrate such as a glass substrate, and it is preferable that the surface of the substrate is flat.

[0378] [2] Drying method After the photosensitive coloring composition is applied to the substrate, the composition is preferably dried using a hot plate, an IR oven, or a convection oven. A reduced pressure drying method in which the composition is dried in a reduced pressure chamber without increasing the temperature may also be used in combination.

[0379] 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.

[0380] [3] Exposure method Exposure is carried out by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating it with a light source of ultraviolet or visible light through this mask pattern. When exposure is carried out using an exposure mask, a method in which the exposure mask is brought close to the coating film of the photosensitive coloring composition, or a method in which the exposure mask is placed at a position away from the coating film of the photosensitive coloring composition and exposure light is projected through the exposure mask may be used. 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.

[0381] In a preferred embodiment of the present invention, when black photospacers 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. 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.

[0382] 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.

[0383] 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.

[0384] The exposure dose is usually 1 mJ / cm 2 More than 5mJ / cm, preferably 5mJ / cm 2 More preferably, 10 mJ / cm 2 or more, typically 300mJ / cm 2 Less than 200 mJ / cm 2 Less than or equal to 150 mJ / cm 2 The following is the result. In the case of the proximity exposure method, the distance between the object to be exposed and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[0385] [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.

[0386] 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.

[0387] 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.

[0388] 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.

[0389] 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.

[0390] [5] Post-exposure and heat-hardening treatment After development, the substrate may be subjected to additional exposure using a method similar to the above exposure method, if necessary, or may be subjected to a thermal curing treatment at a temperature of 100°C to 280°C, preferably 150°C to 250°C, for 5 to 60 minutes.

[0391] The size and shape of the colored spacer of the present invention are adjusted as appropriate depending on the specifications of the color filter to which it is applied, but the photosensitive colored composition of the present invention is particularly useful for simultaneously forming black photospacers by photolithography, in which the spacer and subspacer have different heights. The height of the spacer is usually about 2 to 7 μm, and the height of the subspacer is usually about 0.2 to 1.5 μm shorter than the spacer. Furthermore, from the viewpoint of light-shielding properties, the optical density (OD) per μm of the colored spacer of the present invention is preferably 0.7 or more, more preferably 1.2 or more, even more preferably 1.5 or more, and particularly preferably 1.8 or more, and is usually 4.0 or less, preferably 3.0 or less. For example, 0.7 to 4.0 is preferred, 1.2 to 4.0 is more preferred, 1.5 to 3.0 is even more preferred, and 1.8 to 3.0 is particularly preferred. Here, the optical density (OD) is a value measured by the method described below.

[0392] [Bulkhead] The photosensitive coloring composition of the present invention can be suitably used to form 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.

[0393] The partition walls using the photosensitive coloring composition of the present invention will be described in accordance with the method for producing the same.

[0394] (1) Support As the support and substrate for forming the partition walls, the same support and substrate as those for forming the colored spacers described above can be used.

[0395] (2) Bulkhead Hereinafter, the case where the photosensitive coloring composition of the present invention 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 composition.

[0396] Typically, a photosensitive coloring 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.

[0397] (3) Formation of partitions In the method for forming a partition wall using the photosensitive coloring composition of the present invention, the specific methods of supplying the photosensitive coloring composition to the substrate, drying method, exposure method, development method, additional exposure and heat curing treatment can be the same as those for forming the colored spacer described above.

[0398] 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 coloring composition of the present invention is usually about 0.5 to 10 μm. Furthermore, from the viewpoint of light-shielding properties, the optical density (OD) per 1 μm of the partition walls of the present invention is preferably 0.7 or more, more preferably 1.2 or more, even more preferably 1.5 or more, and particularly preferably 1.8 or more. It is usually 4.0 or less, and preferably 3.0 or less. For example, it is preferably 0.7 to 4.0, more preferably 1.2 to 4.0, even more preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. Here, the optical density (OD) is a value measured by the method described below.

[0399] [Organic electroluminescent device] The organic electroluminescent device of the present invention includes a cured product, such as a partition wall, made of the above-mentioned photosensitive coloring 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.

[0400] 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, 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. 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.

[0401] 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.

[0402] 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.

[0403] 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.

[0404] [Image display device] The image display device of the present invention includes the cured product of the present invention. For example, an alignment film is formed on a liquid crystal driving substrate (array substrate) having colored spacers formed from the photosensitive coloring composition of the present invention, and the alignment film is bonded to a counter electrode substrate to form a liquid crystal cell, and liquid crystal is injected into the formed liquid crystal cell, thereby making it possible to manufacture an image display device such as a liquid crystal display device containing the cured product of the present invention. In addition, a colored spacer formed from the photosensitive coloring composition of the present invention is placed on the counter substrate side, and is bonded to a liquid crystal driving substrate (array substrate) to form a liquid crystal cell, and liquid crystal is injected into the formed liquid crystal cell, thereby making it possible to manufacture an image display device such as a liquid crystal display device containing the cured product of the present invention. As described in Japanese Patent Application Laid-Open No. 2014-215614, the liquid crystal alignment can be improved by using a specific alignment material and irradiating the liquid crystal with ultraviolet light after injecting the liquid crystal into a liquid crystal cell.

[0405] The image display device of the present invention may also 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.

[0406] [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. 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]

[0407] 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 constituent components of the pigment dispersions and photosensitive coloring compositions used in the following examples and comparative examples, as well as the methods for evaluating them, are as follows.

[0408] <Alkali-soluble resin-I> 145 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was stirred while purging with nitrogen and heated to 120°C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of a monomethacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, followed by 8.47 parts by weight of 2,2'-azobis-2-methylbutyronitrile over 3 hours, and stirring was continued for another 2 hours at 90°C. Next, the atmosphere in the reaction vessel was replaced with air, and 43.2 parts by weight of acrylic acid, 0.7 parts by weight of tris(dimethylaminomethyl)phenol, and 0.12 parts by weight of hydroquinone were added, and the reaction was continued for 12 hours at 100°C. Subsequently, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the reaction was continued for 3.5 hours at 100°C. The weight average molecular weight Mw of the obtained alkali-soluble resin-I measured by GPC was 8,400, and the acid value was 80 mgKOH / g.

[0409] <Alkali-soluble resin-II> A reaction vessel was charged with 300 parts by weight of Nippon Kayaku's "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, and the mixture was 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 mixture was reacted at 120°C for 4 hours. The weight-average molecular weight (Mw) of the resulting alkali-soluble resin-II, as measured by GPC, was 2600, and the acid value was 106 mgKOH / g.

[0410] <Pigment-I> CI Pigment Blue 60 <Pigment-II> CI Pigment Orange 64 <Pigment-III> CI Pigment Violet 29 <Pigment-IV> Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (I-1)) manufactured by BASF

[0411] [ka]

[0412] <Dispersant-I> This methacrylic ABA triblock copolymer consists of an A block containing repeating units with solvent-philic groups and a B block containing repeating units with pigment-adsorbing groups. It has repeating units of the following formulas (a) to (g). The amine value is 48 mg KOH / g. The theoretical molecular weight is 8,300.

[0413] The content ratios of the repeating units of the following formulae (a) to (g) in all repeating units are (a) 40.4 mol% (26.6 mass%), (b) 13.7 mol% (12.8 mass%), (c) 9.3 mol% (12.1 mass%), (d) 7.7 mol% (8.9 mass%), (e) 2.7 mol% (4.9 mass%), (f) 17.0 mol% (17.6 mass%), and (g) 9.2 mol% (17.1 mass%), respectively.

[0414] [ka]

[0415] [ka]

[0416] <Dispersant-II> BYK-LPN6919 is a dispersant manufactured by BYK Chemie. It is a methacrylic AB block copolymer consisting of an A block containing repeating units with solvent-philic groups and a B block containing repeating units with pigment-adsorbing groups. It has repeating units of the following formulas (2a) and (3a). Its amine value is 120 mg KOH / g and its acid value is 1 mg KOH / g or less.

[0417] The content of the repeating unit of the following formula (2a) and the repeating unit of the following formula (3a) in all repeating units is 33.3 mol % and 6.7 mol %, respectively.

[0418] [ka]

[0419] <Dispersant-III> 2.92 parts by mass (solid content, PGMEA solution) of Dispersant-II and 0.35 parts by mass of phenylphosphonic acid were mixed and stirred, and the solid content of the resulting mixture was used as Dispersant-III. Dispersant-III is presumed to have repeating units of the following formulae (1a-1), (2a), and (3a): The contents of the repeating units of the following formulae (1a-1), (2a), and (3a) in the total repeating units are 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively.

[0420] [ka]

[0421] <Dispersant-IV> 2.88 parts by mass (solid content, PGMEA solution) of Dispersant-II and 0.38 parts by mass of benzenesulfonic acid monohydrate were mixed and stirred, and the solid content of the resulting mixture was used as Dispersant-IV. Dispersant-IV is presumed to have repeating units of the following formulae (1a-2), (2a), and (3a): The contents of the repeating units of the following formulae (1a-2), (2a), and (3a) in the total repeating units are 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively.

[0422] [ka]

[0423] <Dispersant-V> 2.85 parts by mass of Dispersant-II (solid content, PGMEA solution) and 0.41 parts by mass of p-toluenesulfonic acid were mixed and stirred, and the solid content of the resulting mixture was used as Dispersant-V. Dispersant-V is presumed to have repeating units of the following formulae (1a-3), (2a), and (3a): The contents of the repeating units of the following formulae (1a-3), (2a), and (3a) in the total repeating units are 13.0 mol%, 20.3 mol%, and 6.7 mol%, respectively.

[0424] [ka]

[0425] <Dispersant-VI> A methacrylic AB diblock copolymer consisting of an A block containing a repeating unit with a solvent-philic group and a B block containing a repeating unit with a pigment-adsorbing group. It has repeating units of the following formulas (h) to (n). The amine value is 70 mg KOH / g.

[0426] 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) 22.2 mol%, and (n) 11.1 mol%, respectively.

[0427] [ka]

[0428] [ka]

[0429] <Dispersant-VII> 2.90 parts by mass of Dispersant-II (solid content, PGMEA solution) and 0.37 parts by mass of methyl p-toluenesulfonate were mixed and stirred, and the solid content of the resulting mixture was used as Dispersant-VII. Dispersant-VII is presumed to have repeating units of the following formulae (1a-5), (2a), and (3a): The contents of repeating units of the following formulae (1a-4), (2a), and (3a) in the total repeating units are 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively.

[0430] [ka]

[0431] <Solvent-I> PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II> MB: 3-methoxy-1-butanol

[0432] <Photopolymerization initiator-I> Oxime ester photopolymerization initiator with the following chemical structure

[0433] [ka]

[0434] <Photopolymerization initiator-II> Oxime ester compounds with the following chemical structure (4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoic acid methyl ester

[0435] [ka]

[0436] <Ethylenically unsaturated compounds> DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Surfactant> DIC Megafack F-559 <Additives> Nippon Kayaku KAYAMER PM-21 (phosphate containing methacryloyl group)

[0437] <Viscosity evaluation> The viscosity of the prepared pigment dispersion was measured using a RE-85L viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23° C., 20 rpm).

[0438] <Measurement of optical density per unit film thickness (unit OD value)> The optical density per unit film thickness was measured by the following procedure. First, the prepared photosensitive coloring composition was applied to a glass substrate using a spin coater so that the film thickness after heat curing would be 3.0 μm, and after drying under reduced pressure for 1 minute, it was dried on a hot plate at 90 ° C for 140 seconds. The obtained coating film was exposed to light without using an exposure mask. The irradiation light source had an intensity of 45 mW / cm at a wavelength of 365 nm. 2 A high-pressure mercury lamp was used, and the exposure dose was 50 mJ / cm 2 Subsequently, the resist was cured by heating in an oven at 230° C. for 20 minutes, thereby obtaining a resist-coated substrate 1. The optical density (OD value) of the obtained resist-coated substrate 1 was measured using an X-Rite 361T(V) transmission densitometer (color temperature of illumination light source: approximately 2850K (equivalent to CIE standard illuminant A), spectral sensitivity characteristics of the light-receiving section: ISO visual density according to ISO 5-3 standard). The film thickness was measured using a non-contact surface / layer cross-sectional shape measurement system, VertScan(R) 2.0, manufactured by Ryoka Systems Co., Ltd., and the optical density (unit OD value) per unit film thickness (1 μm) was calculated from the optical density (OD value) and film thickness. The OD value is a value that indicates the light-blocking ability, with a higher value indicating a higher light-blocking ability.

[0439] <Evaluation of voltage holding ratio (VHR) and ion density> Each photosensitive coloring composition was applied to an electrode substrate having an ITO film formed on one side, dried in vacuum for 1 minute, and then dried on a hot plate at 90°C for 140 seconds. The resulting coating film was irradiated with 50 mJ / cm using a high-pressure mercury lamp. 2 , illuminance 45mW / cm 2 The substrate was subjected to image exposure under the following exposure conditions: Next, shower development was performed at 25°C using an approximately 0.05% by mass aqueous potassium hydroxide solution at 25°C under a water pressure of 0.15 MPa, after which development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted to between 10 and 20 seconds, and was approximately 1.6 times the time (break time) required for the unexposed photosensitive coloring composition layer to dissolve and be removed. Subsequently, the substrate was heated and cured in an oven at 230°C for 20 minutes to obtain an electrode substrate for evaluation. Otherwise, empty cells were prepared using the method described in WO 2018 / 151079. Liquid crystal (MLC-6608 manufactured by Merck Japan) was poured into the empty cell, and the periphery was sealed with a UV-curable sealant. The liquid crystal cell was then annealed (heated at 105°C for 2.5 hours in a hot air circulating oven) to prepare a liquid crystal cell for measurement.

[0440] A voltage of 5 V was applied to the fabricated liquid crystal cell for measurement under the conditions of 0.6 Hz and a frame time of 1667 msec, and the voltage holding ratio before ultraviolet irradiation was measured using a "Liquid Crystal Physical Property Evaluation Apparatus - Model 6254" manufactured by Toyo Technica Co., Ltd. The voltage holding ratio is an index of electrical reliability. Also, a higher voltage holding ratio is more preferable. Then, using the same apparatus, the current when a triangular wave of 0.1 Hz and ±3 V was applied to the liquid crystal cell for measurement was measured over time, and a waveform of the time change of the current was obtained. The area of the impurity ion peak in the waveform was measured, and the ion density (pC) before ultraviolet irradiation was measured.

[0441] Next, the liquid crystal cell for measurement was irradiated with ultraviolet light using a high-pressure mercury lamp at 18 J / cm 2 , an illuminance of 40 mW / cm 2 . Using the liquid crystal cell for measurement after the ultraviolet irradiation, the voltage holding ratio and the ion density after ultraviolet irradiation were measured in the same procedure as described above.

[0442] <NMP Resistance Evaluation> The N-methylpyrrolidone (NMP) resistance evaluation was performed according to the following procedure. First, the prepared photosensitive coloring composition was applied to an IZO substrate using a spin coater so that the film thickness after heat curing would be 3.0 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 90 °C for 140 seconds. The obtained coated film was exposed without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp with an intensity of 45 mW / cm at a wavelength of 365 nm was used, and the exposure amount was 50 mJ / cm 2 . 2Next, 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 25°C under a water pressure of 0.05 MPa. Development was then stopped with pure water and the substrate was washed with a water spray. The shower development time was set to 1.6 times the time required for the unexposed coating film to be dissolved and removed, which was previously measured. The substrate was then heated and cured in an oven at 230°C for 20 minutes to obtain resist-coated substrate 2. Two measurement substrates (2.5 cm x 1.0 cm square) were cut from the prepared resist-coated substrate 2 and immersed in a 10 mL vial containing 8 mL of NMP. The vial containing the measurement substrate was then placed in a heat bath at 80°C for 40 minutes, and an NMP elution test was performed. After leaving the vial to stand for 40 minutes, the vial was removed from the heat bath, and the absorbance of the NMP elution solution was measured at 1 nm intervals over the wavelength range of 300 to 800 nm using a spectrophotometer (Shimadzu UV-3100PC). A halogen lamp and a deuterium lamp (switchable wavelength 360 nm) were used as the light source, and a photomultiplier was used as the detector, with a slit width of 2 nm. The sample solution (NMP elution solution) was placed in a 1 cm square quartz cell for measurement. In spectroscopy, absorbance is a dimensionless quantity that indicates the degree to which light intensity is attenuated when light passes through an object, and is defined by the following equation:

[0443] A(absorbance)=-log 10 (I / I0) (I: transmitted light intensity, I0: incident light intensity)

[0444] Furthermore, when light is irradiated from the same light source onto the sample solution and the NMP solution, the light intensity transmitted through the NMP solution can be considered as I0 and the light intensity transmitted through the sample solution as I. Therefore, (I / I0) in the above equation represents the light transmittance, and absorbance A is the logarithmic representation of the reciprocal of transmittance. Absorbance A is a notation used to calculate the concentration of substances contained in the sample solution. Absorbance A = 0 indicates no light absorption (100% transmittance), while absorbance A = ∞ indicates no light transmission (0% transmittance). In other words, the higher the absorbance, the more resist coating components have dissolved into the NMP, indicating poor NMP resistance. The spectral area of ​​the measured absorbance was calculated and the NMP resistance was evaluated according to the following criteria. The spectral area of ​​the absorbance, which is the evaluation criterion, can be expressed as the sum of the absorbance at each wavelength, meaning the total amount of dissolved resist components.

[0445] NMP resistance evaluation criteria: Judgment based on the absorbance spectrum area value (wavelength 300-800 nm) A: 100 or less B: Over 100 and under 200 C: Over 200

[0446] <Preparation of pigment dispersions 1 to 7> 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 dispersions 1 to 7. The amount of solvent in Table 1 includes the amount of solvent derived from the dispersant and alkali-soluble resin. Table 1 also shows the evaluation results of the viscosity of the pigment dispersion liquid measured by the above-mentioned method.

[0447] [Table 1]

[0448] [Examples 1 to 4, Comparative Examples 1 to 6] 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 further added so that the total solid content was 22% by mass, and the mixture was stirred and dissolved to prepare the photosensitive coloring compositions of Examples 1 to 4 and Comparative Examples 1 to 6. Table 2 also shows the evaluation results of the unit OD value, voltage holding ratio (VHR), ion density, and NMP resistance measured by the above-mentioned methods.

[0449] [Table 2]

[0450] As can be seen from Table 2, in the photosensitive coloring composition of Comparative Example 4, the counter ion in the repeating unit represented by the above formula (1) in Dispersant-VI was a halogen ion, not a counter anion represented by the above formula (2), and therefore the voltage holding ratio after UV irradiation, ion density, and NMP resistance were all significantly inferior. On the other hand, the photosensitive coloring composition of Comparative Example 5 had an optical density per unit film thickness of less than 0.5, which was good even without the dispersant described in the present application, and did not encounter the problems of the present application. This is presumably because Comparative Example 5 had fewer impurities in the pigment, less free counter anions in the dispersant, etc. The photosensitive coloring composition of Comparative Example 1 had significantly poor NMP resistance. Dispersant-III contained in the photosensitive coloring composition of Comparative Example 1 has a counter anion of the ammonium group that forms a salt with a phosphonate ion derived from a weak acid, but because it is derived from a weak acid, it is easy to return to the phosphonic acid and amino group, and when immersed in an amine-based solvent such as NMP, the compatibility of the dispersant is high, and the dispersant is easily released from the colorant, so that the dispersant adsorbed and covering the surface of the colorant is reduced, and it is presumed that part of the colorant is eluted as an impurity.

[0451] On the other hand, in the photosensitive coloring compositions of Comparative Examples 2 and 3, the voltage holding ratio before ultraviolet irradiation was low, and the voltage holding ratio was even lower after ultraviolet irradiation. This is because the toluenesulfonate anion and benzenesulfonate anion, which are counter anions of the ammonium groups of Dispersants-IV and V contained in the photosensitive coloring compositions of Comparative Examples 2 and 3, are both stable anions derived from strong acids, so the sulfonate anions of the excess dispersant that are not adsorbed to the pigment dissolve in the liquid crystal, lowering the voltage holding ratio, and further increasing the counter anions liberated by ultraviolet irradiation, further lowering the voltage holding ratio.

[0452] In addition, the photosensitive coloring composition of Comparative Example 6 had a low voltage holding ratio before UV irradiation, and the voltage holding ratio was even lower after UV irradiation. This is presumably because methyl toluenesulfonate contained in Dispersant-VI in the photosensitive coloring agent of Comparative Example 6 is easily liberated, and was further liberated by UV irradiation, dissolving into the liquid crystal and reducing the voltage holding ratio.

[0453] On the other hand, the photosensitive coloring composition of Example 1 had good NMP resistance, and both the voltage holding ratio before and after ultraviolet irradiation were good. This is presumably because the counter anion represented by the general formula (2) of the dispersant-I contained in the photosensitive coloring composition of Example 1 is not an anion derived from an acid but an anion derived from an ester, so that the ammonium group does not return to an amino group, and the NMP resistance is good. Furthermore, this counter anion is an ester-derived anion that is stably bonded to the ammonium group. Therefore, even if excess dispersant remains in the cured product, it is unlikely to be liberated as an anion into the liquid crystal, and therefore is unlikely to affect the alignment of the liquid crystal. It is presumed that this is why the voltage holding ratio was good both before and after UV irradiation.

[0454] Furthermore, as in the case of the photosensitive coloring composition of Example 3, the lower the unit OD, the better the voltage holding ratio and NMP resistance. This is presumably due to the fact that there is less elution of impurities from the pigment. Furthermore, as in the case of the photosensitive coloring compositions of Examples 2 and 4, even when the organic black pigment of structural formula (1) is contained, the voltage holding ratio and NMP resistance were good.

Claims

1. A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more, A photosensitive coloring composition, wherein the dispersant (f) contains a dispersant (f1) having a repeating unit represented by the following general formula (1): 【Chemistry 1】 (In formula (1), R 1 ~R 3 are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 ~R 3 Two or more of these may be bonded to each other to form a ring structure. R 4 is a hydrogen atom or a methyl group. X is a divalent linking group. Y - is a counter anion represented by the following general formula (2): 【Chemistry 2】 (In formula (2), R 5 represents an alkyl group which may have a substituent.

2. The photosensitive coloring composition according to claim 1, wherein the (a) colorant comprises at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment.

3. The photosensitive coloring composition according to claim 1 or 2, wherein the colorant (a) includes a black pigment.

4. The photosensitive coloring composition of claim 3 , wherein the black pigment comprises an organic black pigment.

5. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the content of the colorant (a) is 10 mass% or more of the total solid content.

6. The photosensitive coloring composition according to any one of claims 1 to 5, wherein the amine value of the dispersant (f1) is 30 mg KOH / g or more.

7. The photosensitive coloring composition according to any one of claims 1 to 6, which is used for forming a colored spacer.

8. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7.

9. An image display device comprising the cured product according to claim 8.

10. A pigment dispersion for an image display device, comprising: (a) a colorant; (e) a solvent; and (f) a dispersant, the colorant (a) contains a black pigment, A pigment dispersion for an image display device, wherein the dispersant (f) contains a dispersant (f1) having a repeating unit represented by the following general formula (1): 【Transformation 3】 (In formula (1), R 1 ~R 3 are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 ~R 3 Two or more of these may be bonded to each other to form a ring structure. R 4 is a hydrogen atom or a methyl group. X is a divalent linking group. Y - is a counter anion represented by the following general formula (2): 【Chemistry 4】 (In formula (2), R 5 represents an alkyl group which may have a substituent.

11. The pigment dispersion for an image display device according to claim 10 , wherein the black pigment comprises an organic black pigment.

12. The pigment dispersion for an image display device according to claim 10 or 11, wherein the dispersant (f1) has an amine value of 30 mgKOH / g or more.

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