Photosensitive colored composition, cured product, image display device, and pigment dispersion 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 colored composition, a cured product, an image display device, and a pigment dispersion for an image display device. More specifically, the present invention relates to a photosensitive colored composition used for forming a colored spacer in an image display device for liquid crystal displays, a cured product obtained by curing the photosensitive colored composition, and an image display device containing the cured product. This application claims priority based on Japanese Patent Application No. 2019-162547, filed in Japan on September 6, 2019, and Japanese Patent Application No. 2020-026622, filed in Japan on February 19, 2020, and the contents thereof are incorporated herein by reference. [Background technology]

[0002] Liquid crystal displays (LCDs) utilize the property that the arrangement of liquid crystal molecules changes when voltage is switched on and off to the liquid crystal. On the other hand, many of the components that make up an LCD cell are formed using methods that utilize photosensitive compositions, such as photolithography. Because these photosensitive compositions can easily form fine structures and are easy to process on substrates for large screens, their range of application is expected to expand further in the future.

[0003] However, LCDs manufactured using photosensitive compositions may experience problems such as uneven display due to the inability to maintain the voltage applied to the liquid crystal, caused by the electrical properties of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition. This effect is particularly significant in components closer to the liquid crystal layer in color liquid crystal displays, such as so-called columnar spacers or photospacers used to maintain a constant distance between two substrates in a liquid crystal panel.

[0004] Conventionally, when using spacers that do not have light-shielding properties with TFT-type LCDs, the light transmitted through the spacer could cause the TFT, which acts as a switching element, to malfunction. To prevent this, methods using light-shielding spacers (colored spacers) are being considered.

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

[0006] Patent Document 2 discloses a colored composition that exhibits excellent light-shielding properties in the visible light region and transmittance in the near-infrared region by using a specific coloring agent in combination with a dispersant having an amino group of a specific structure.

[0007] Patent Document 3 discloses that block copolymers having a specific anion exhibit 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 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] With recent changes in panel structure, methods of irradiating liquid crystal cells with ultraviolet light after fabrication to improve liquid crystal alignment are becoming more widespread. When ultraviolet light is irradiated, some of the pigments contained in colored spacers and other components tend to decompose, generating impurities, and it is required to maintain sufficient electrical reliability even in such cases.

[0010] When the present inventors investigated a photosensitive colored composition containing a dispersant described in Patent Document 1, they found it difficult to ensure electrical reliability after UV irradiation. The photosensitive colored composition containing the dispersant described in Patent Document 2 had insufficient chemical resistance (NMP resistance) to the solvent (N-methylpyrrolidone, NMP) used when forming the alignment film. The photosensitive colored composition containing a dispersant described in Patent Document 3 had difficulty ensuring electrical reliability both before and after UV irradiation.

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

[0012] As a result of diligent research by the inventors, it was discovered that the above problems could be solved by using a specific dispersant, leading to the completion of the present invention. In other words, the gist of this invention is as follows.

[0013] [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 per 1 μm of film thickness of the cured coating is 0.5 or higher. A photosensitive colored composition characterized in that the (f) dispersant contains a dispersant (f1) having repeating units represented by the following general formula (1).

[0014] [ka]

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

[0016] [ka]

[0017] (In formula (2), R 5 (This is an alkyl group which may have substituents.)

[0018] [2] The photosensitive coloring composition according to [1], wherein the coloring agent (a) comprises 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. [3] The photosensitive coloring composition according to [1] or [2], wherein the coloring agent (a) comprises 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 coloring agent (a) is 10% by mass or more in the total solid content. [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the amine value of the dispersant (f1) is 30 mg KOH / g or more.

[0019] [7] A photosensitive colored composition according to any one of [1] to [6] for forming a colored spacer. [8] A cured product obtained by curing any of the photosensitive coloring compositions described in [1] to [7]. [9] An image display device containing the cured material described in [8].

[0020]

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

[0021]

Chemical Formula

[0022] (In formula (1), R 1 to R 3 each independently represent an optionally substituted alkyl group or an optionally substituted aryl group, and two or more of R 1 to R 3 may be bonded to each other to form a cyclic 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]

Chemical Formula

[0024] (In formula (2), R 5 is an optionally substituted alkyl group.)

[0025]

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

[10] , wherein the black pigment comprises 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.

Advantageous Effects of Invention

[0026] According to the present invention, there can be provided a photosensitive colored composition that is excellent in electrical reliability after ultraviolet irradiation and has good solvent resistance.

Mode for Carrying Out the Invention

[0027] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below and can be implemented with various modifications within the scope of its gist. In this invention, "(meth)acrylic" means "acrylic and / or methacrylic," and the same applies to "(meth)acrylate" and "(meth)acryloyl."

[0028] "(Co)polymer" means that it includes both monopolymers (homopolymers) and copolymers, and "acid (anhydride)" and "(anhydride)...acid" mean that it includes both the acid and its anhydride. In the present invention, "acrylic resin" means a (co)polymer containing (meth)acrylic acid, or a (co)polymer containing a (meth)acrylic acid ester having a carboxyl group.

[0029] In this invention, "monomer" is a term used in contrast to so-called polymers, and includes not only monomers in the narrow sense, but also dimers, trimers, and oligomers. In the present invention, "total solids" means all components other than the solvent contained in the photosensitive coloring composition or pigment dispersion. In this invention, "weight-average molecular weight" means the weight-average molecular weight (Mw) calculated on a polystyrene basis by GPC (gel permeation chromatography). In this invention, unless otherwise specified, "amine value" refers to the amine value on an effective solids basis, and is expressed as the amount of base and the mass of equivalent KOH per gram of solids of the dispersant. The measurement method will be described later. Unless otherwise specified, "acid value" refers to the acid value on an effective solids basis, and is calculated by neutralization titration.

[0030] Regarding pigments, "CI" stands for Color Index.

[0031] In this specification, percentages and parts expressed in "mass" are synonymous with percentages and parts expressed in "weight".

[0032] [Photosensitive coloring composition] The photosensitive coloring composition of the present invention is (a) Colorants (b) Alkali-soluble resins (c) Photopolymerization initiator (d) Ethylene unsaturated compounds (e) solvent (f) Dispersant It contains as an essential component, and optionally includes other components such as adhesion enhancers like silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors. Typically, each component is used in a state where it is dissolved or dispersed in a solvent.

[0033] (a) Colorants The photosensitive colored composition of the present invention contains (a) a coloring agent. By containing (a) a coloring agent, appropriate light absorption can be obtained, and in particular, appropriate light shielding when used for applications such as forming light-shielding members such as colored spacers. Furthermore, the photosensitive colored 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 coloring agent and setting the OD per unit film thickness to be above the lower limit, the light-shielding properties of the resulting cured product, in particular the colored spacer, are improved.

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

[0035] The type of colorant that can be used in the photosensitive colored composition of the present invention is not particularly limited, and pigments or dyes may be used. Among these, pigments are preferred from the viewpoint of durability.

[0036] (a) The pigment contained in the colorant may be one type or two or more types. In particular, from the viewpoint of achieving both uniform light shielding in the visible region and OD per unit film thickness, it is preferable to have two or more types. (a) The types of pigments that can be used as colorants are not particularly limited, but examples include organic colorants and black pigments. Here, organic colorants refer to organic pigments that exhibit colors other than black, and examples include red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

[0037] Among pigments, organic coloring pigments are preferable from the viewpoint of suppressing the absorption of ultraviolet light and making it easier to control the shape and unevenness of the cured product. Furthermore, from the viewpoint of light shielding, black pigments are preferable.

[0038] Organic coloring pigments may be used individually or in combination of two or more. In particular, from the viewpoint of achieving an OD of 0.5 or more per unit film thickness, it is more preferable to use a combination of organic coloring pigments of different colors, and even more preferable to use a combination of organic coloring pigments that exhibit a color close to black.

[0039] The chemical structures of these organic coloring pigments are not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolon, isoindolinone, dioxazine, indanthrene, and perylene pigments. Specific examples of usable pigments are shown below by their pigment numbers. In the following examples such as "CI Pigment Red 2," "CI" stands for Color Index.

[0040] As for red pigments, 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, 23 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 can be listed. Among these, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254 are preferred from the viewpoint of light shielding and dispersion, and CI Pigment Red 177, 209, 224, and 254 are even more preferred. Furthermore, in terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Red 177, 254, and 272. When curing the photosensitive colored composition with ultraviolet light, it is preferable to use a red pigment with a low ultraviolet absorption rate, and from this viewpoint, it is even more preferable to use CI Pigment Red 254 and 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, CI Pigment Orange 13, 43, 64, and 72 are preferred from the viewpoint of dispersibility and light-shielding properties. When curing a photosensitive colored composition with ultraviolet light, it is preferable to use an orange pigment with a low ultraviolet absorption rate, and from this viewpoint, CI Pigment Orange 64 and 72 are more preferable.

[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-shielding properties, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and CI Pigment Blue 15:6 is even more preferred. Furthermore, in terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Blue 15:6, 16, or 60. When curing the photosensitive colored composition with ultraviolet light, it is preferable to use a blue pigment with a low ultraviolet absorption rate, and from this viewpoint, it is even 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-shielding properties, CI Pigment Violet 19, 23, and 29 are preferred, and CI Pigment Violet 23 is even more preferred. Furthermore, in terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Violet 23 and 29. When curing the photosensitive colored composition with ultraviolet light, it is preferable to use a purple pigment with a low ultraviolet absorption rate, and 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. Among these, CI Pigment Green 7 and 36 are preferred. As for yellow pigments, 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 We can list 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. Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferred, and even more preferred are CI Pigment Yellow 83, 138, 139, 150, and 180.

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

[0046] Among these, it is preferable to include at least one of the following pigments from the viewpoint of light shielding properties of the cured product and control of shape and steps. Red pigments: 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 using two or more organic coloring pigments in combination, there are no particular limitations on the combination of organic coloring pigments, but from the viewpoint of light shielding, it is preferable to include 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. While there are no particular limitations on the color combinations, from the standpoint of light-blocking properties, examples include combinations of red and blue pigments, blue and orange pigments, and blue, orange, and purple pigments.

[0048] Examples of black pigments include organic black pigments and inorganic black pigments. Of these, organic black pigments are preferred because they suppress the absorption of ultraviolet light, making it easier to control the shape and unevenness of the cured product. Among organic black pigments, it is preferable to use an organic black pigment (hereinafter sometimes referred to as "organic black pigment represented by general formula (1)") that includes 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 of these independently represents a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom; R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 Each of them independently consists of a hydrogen atom, a halogen atom, and 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 , NR 21 R 22 NHCOR 22 , NR 21 COR 22 N=CH2, N=CHR 21 N=CR 21 R 22 SH, SR 21 SOR 21 SO2R 21 SO3R 21 SO3H, SO3 - SO2NH2, SO2NHR 21 or SO2NR 21 R 22 It 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 At least one combination selected from the group consisting of these elements may be directly bonded to each other, or it may consist of an oxygen atom, a sulfur atom, NH, or NR. 21 They may be connected to each other by bridges; R 21 and R 22 Each of these 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 its geometric isomers have the following core structures (with substituents omitted in the structural formulas), and the trans-trans isomer is probably the most stable.

[0052] [ka]

[0053] If compound (1) is anionic, it is preferable that its charge is compensated by any known suitable cation, such as a metal, organic, inorganic, or metal-organic cation, specifically alkali metals, alkaline earth metals, transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Furthermore, if the geometric isomer of compound (1) is anionic, it is preferable that it be a similar salt.

[0054] In the substituents of general formula (1) and their definitions, the following are preferred because they tend to increase the shielding rate. This is because the following substituents do not absorb and are not thought to affect the hue of the pigment. R 12 , R 14 , R 15 , R 17 , R 19and R 20 each independently is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom. R 13 and R 18 each independently is 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 - , more preferably a hydrogen atom or SO3H, and particularly preferably a hydrogen atom.

[0055] R 11 and R 16 each independently is preferably a hydrogen atom, CH3 or CF3, and 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 is identical; more preferably, R 11 is identical to R 16 , R 12 is identical to R 17 , R 13 is identical to R 18 , R 14 is identical to R 19 , and R 15 is identical to R 20 .

[0056] C1-C12 alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl, or dodecyl groups.

[0057] Examples of cycloalkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thuzyl, norbornyl, bornyl, norcalyl, calyl, menthyl, norpinyl, pinyl, adamantane-1-yl, or adamantane-2-yl groups.

[0058] Alkenyl groups having 2 to 12 carbon atoms include, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-menthyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadiene-3-yl, hexenyl, octenyl, nonenyl, decenyl, or dodecenyl groups.

[0059] Examples of cycloalkenyl groups having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadiene-1-yl, 1-p-menten-8-yl, 4(10)-thujen-10-yl, 2-norbornene-1-yl, 2,5-norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaladien-3-yl, or camphenyl.

[0060] Alkynyl groups having 2 to 12 carbon atoms include, for example, 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butyne-2-yl group, 1,4-pentadiiin-3-yl group, 1,3-pentadiiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-in-1-yl group, trans-3-methyl-2-penten-4-in-1-yl group, 1,3-hexadiiin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decine-10-yl group, or 1-dodecine-12-yl group.

[0061] Halogen atoms include, for example, fluorine, chlorine, bromine, or iodine atoms.

[0062] The organic black pigment represented by the general formula (1) is preferably an organic black pigment that includes at least one selected from the group consisting of a compound represented by the general formula (2) below (hereinafter also referred to as "compound (2)") and geometric isomers of compound (2).

[0063] [ka]

[0064] An example of such an organic black pigment is Irgaphor® Black S 0100 CF (manufactured by BASF), which is sold under the trade name. This organic black pigment is preferably dispersed and used by a dispersant, solvent, and method described later. Furthermore, the presence of sulfonic acid derivatives of compound (1), particularly sulfonic acid derivatives of compound (2), during dispersion may improve dispersibility and storage properties; therefore, 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) above include aniline black and perylene black.

[0066] On the other hand, from the viewpoint of light-shielding properties, it is preferable to use inorganic black pigments. 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:

[0067] Mitsubishi Chemical Corporation products: 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, same hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, same 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, same hereinafter) XC72R, ELFTEX (registered trademark)-8 Manufactured by Biller: RAVEN (registered trademark, same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0068] Carbon black coated with resin may be used. Using resin-coated carbon black has the effect of improving adhesion to the glass substrate and volume resistivity. As an example of resin-coated carbon black, the carbon black described in Japanese Patent Publication No. 09-71733 can be suitably used. Resin-coated carbon black is suitably used in terms of volume resistivity and dielectric constant.

[0069] For carbon black used in resin coating, it is preferable that the total content of Na and Ca is 100 ppm or less. Carbon black typically contains Na and ash composed of Ca, K, Mg, Al, Fe, etc., in percentages, which are mixed in from raw material oil and combustion oil (or gas) during manufacturing, reaction stop water and granulation water, and even furnace materials of the reactor. Of these, Na and Ca are generally present in amounts of several hundred ppm or more, but reducing these amounts tends to suppress penetration into transparent electrodes (ITO) and other electrodes, thereby preventing electrical short circuits.

[0070] Methods to reduce the ash content containing these Na and Ca include carefully selecting raw materials, fuel oil (or gas), and reaction stop water with the lowest possible Na and Ca content when manufacturing carbon black, and minimizing the amount of alkaline substances added to adjust the structure. Another method involves washing the carbon black produced from the furnace with water or hydrochloric acid to dissolve and remove the Na and Ca.

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

[0072] Furthermore, the resin-coated carbon black is preferably so-called acidic carbon black with a pH of 6 or less. This is preferable because it reduces the dispersion diameter (aglomylate diameter) in water, allowing for coating even fine units. In addition, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 ml / 100 g or less. By keeping these parameters within the above range, a coating film with good light-shielding properties tends to be obtained. The average particle diameter refers to the number-average particle diameter, which is the equivalent circle diameter obtained by particle image analysis, in which several fields of view are captured using an electron microscope at tens of thousands of times magnification, and approximately 2000 to 3000 particles in these images are measured using an image processing device.

[0073] There are no particular limitations on the method for preparing resin-coated carbon black, but for example, after appropriately adjusting the proportions of carbon black and resin, 1. a resin solution obtained by mixing resin with a solvent such as cyclohexanone, toluene, or xylene and heating and dissolving it, and a suspension of carbon black and water are mixed and stirred, the carbon black and water are separated, the water is removed, and the mixture is heated and kneaded to obtain a composition which is then formed into a sheet, pulverized, 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, the resulting granules are separated and heated to remove the remaining solvent Methods for removing the agent and water; 3. Dissolving a carboxylic acid such as maleic acid or fumaric acid in the solvent exemplified above, adding carbon black, mixing and drying, removing the solvent to obtain carboxylic acid-impregnated carbon black, and then adding a resin to dry blend thereto; 4. Preparing a suspension by rapidly stirring a reactive group-containing monomer component constituting the resin to be coated with water, polymerizing and then cooling to obtain a reactive group-containing resin from the polymer suspension, then adding carbon black and kneading to react the carbon black with the reactive group (grafting the carbon black), cooling and grinding; etc. can be employed.

[0074] While there are no particular limitations on the type of resin used for coating, synthetic resins are common, and resins containing a benzene ring in their structure are preferred from the standpoint of dispersibility and dispersion stability because they exhibit stronger amphoteric surfactant properties. Specific synthetic resins that can be used include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, and alkylbenzene resins, as well as thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamide-imide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone. The amount of resin coating over the carbon black is preferably 1 to 30% by mass relative to the total amount of carbon black and resin, and it tends that sufficient coating can be achieved by setting it above the lower limit. On the other hand, it tends that adhesion between resins can be prevented and good dispersibility can be achieved by setting it below the upper limit.

[0075] Carbon black coated with resin in this manner can be used as a light-shielding material for colored spacers according to conventional methods, and color filters using these colored spacers as components can be manufactured according to conventional methods. Using such carbon black tends to result in colored spacers with high light-shielding rates and low surface reflectivity at low cost. Furthermore, it is presumed that coating the carbon black surface with resin also has the effect of encapsulating Ca and Na within the carbon black.

[0076] These pigments are preferably used in a dispersed manner such that the average particle size is typically 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the basis for the average particle size is the number of pigment particles. In the photosensitive colored composition of the present invention, the average particle size of the pigment is determined from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is performed on a sufficiently diluted photosensitive colored composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass; however, if there is a concentration recommended by the measuring instrument, that concentration should be followed) and measured at 25°C.

[0077] Furthermore, in the photosensitive colored composition of the present invention, one type of coloring agent, such as an organic coloring pigment or a black pigment, may be used alone, or two or more types may be used in combination. Of these, it is preferable to use an organic black pigment and an organic coloring pigment in combination from the viewpoint of making it easier to control the shape and steps, while it is preferable to use carbon black and an organic coloring pigment in combination from the viewpoint of light shielding.

[0078] In addition to the organic coloring pigments and black pigments mentioned above, dyes may also be used. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0079] Examples of anthraquinone dyes include CI Bat 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, quinone imine 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 used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, and examples include epoxy (meth)acrylate resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolac resins, and polyvinylphenol resins. (b1) Epoxy (meth)acrylate resin (b2) Acrylic copolymer resin These are preferably used from the standpoint of excellent plate-making properties. They can be used individually or in combination of multiple 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 carboxyl group in the ester portion, and then reacting the resulting hydroxyl group with a compound having two or more substituents that can react with hydroxyl groups, such as a polybasic acid and / or its anhydride. Furthermore, resins obtained by reacting a compound having two or more substituents that can react with hydroxyl groups with the polybasic acid and / or its anhydride before reacting with the polybasic acid and / or its anhydride are also included in the above (b1) epoxy (meth)acrylate resins.

[0082] Furthermore, resins obtained by reacting the carboxyl groups of the resin obtained in the above reaction with a compound having a further reactive functional group are also included in the above (b1) epoxy (meth)acrylate resins. Thus, epoxy (meth)acrylate resins do not substantially contain epoxy groups in terms of their chemical structure and are not limited to "(meth)acrylate," but since epoxy compounds (epoxy resins) are used as raw materials and "(meth)acrylate" is a representative example, they are named in this way according to convention.

[0083] In the present invention, the epoxy (meth)acrylate resin used is preferably (b1-1) and / or epoxy (meth)acrylate resin (b1-2) described below (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin"), 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 carboxyl 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 carboxyl group to an epoxy resin, and then reacting it with a polyhydric alcohol and a polybasic acid and / or its anhydride.

[0085] Here, the term epoxy resin includes the raw material compounds before the resin is formed by thermal curing, 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 two or more phenolic hydroxyl groups, and may be a monomer or a polymer. Suitable types of epoxy resins used as raw materials include, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resins that are reaction products of a polyaddition reaction between dicyclopentadiene and phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resin, and fluorene type epoxy resin. Among these, those having aromatic rings in the main chain are more preferably used.

[0086] Furthermore, examples of epoxy resins include bisphenol A type epoxy resins (e.g., "jER(registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76℃)), and bisphenol F type resins (e.g., " Epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (e.g., "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S type epoxy resins, biphenyl glycidyl ether (e.g., "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins (e.g., "EP" manufactured by Nippon Kayaku Co., Ltd.) PN-201, Mitsubishi Chemical's "EP-152", "EP-154", Dow Chemical's "DEN-438", (o,m,p-)cresol novolac type epoxy resin (e.g., Nippon Kayaku's "EOCN(registered trademark, same below)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (e.g., Nissan Chemical's "TEPIC(registered trademark)"), trisphenolmethane type epoxy resin (e.g., Nippon Kayaku's "EPPN(registered trademark)") The following can be suitably used: registered trademarks (hereinafter the same) -501, EPPN-502, EPPN-503), alicyclic epoxy resins (Daicel Corporation's "Celoxide (registered trademark, hereinafter the same) 2021P", "Celoxide EHPE"), epoxy resins obtained by glycidylating phenolic resins produced by the reaction of dicyclopentadiene and phenol (for example, DIC Corporation's "EXA-7200", Nippon Kayaku Co., Ltd.'s "NC-7300"), and epoxy resins represented by the following general formulas (B1) to (B4).Specifically, examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B1), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B2), "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. as the epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. as the epoxy resin represented by the following general formula (B4).

[0087] [ka]

[0088] In the above general formula (B1), a is the mean value and represents a number between 0 and 10, R 111 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C10 cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group. Note that there are multiple R groups present in one molecule. 111 These may be the same or different.

[0089] [ka]

[0090] In the above general formula (B2), b1 and b2 are each independent mean values, representing numbers from 0 to 10, and R 121 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C10 cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group. Note that there are multiple R groups present in one molecule. 121 These 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 formulas (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 Each of these independently represents an optionally substituted adamantyl group, a hydrogen atom, an optionally substituted C1-C12 alkyl group, or an optionally substituted phenyl group, and * represents a bond.

[0095] [ka]

[0096] In the general formula (B4) above, p and q each independently represent integers from 0 to 4, and R 141 and R 142 Each of these independently represents an alkyl group or halogen atom having 1 to 4 carbon atoms, R 143 and R 144 Each of the following independently represents an alkylene group with 1 to 4 carbon atoms, and x and y independently represent integers of 0 or greater.

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

[0098] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, and 2-(meth)acryloyloxypropyl tetrahydrophthalic acid. Examples include leuloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid (meth), monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid, monomers obtained by adding acids (anhydrides) such as (anhydride) succinic acid, (anhydride) phthalic acid, and (anhydride) maleic acid to hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate, and (meth)acrylic acid dimers. Of these, (meth)acrylic acid is particularly preferred in terms of sensitivity.

[0099] Known methods can be used to add an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150°C in the presence of an esterification catalyst. As esterification catalysts used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

[0100] Furthermore, the epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used individually or in combination of two or more components. The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is preferably in the range of 0.5 to 1.2 equivalents, and more preferably in the range of 0.7 to 1.1 equivalents, per equivalent of epoxy groups in the epoxy resin. By using an amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group above the lower limit, insufficient introduction of unsaturated groups can be suppressed, and the subsequent reaction with polybasic acids and / or their anhydrides tends to be sufficient. On the other hand, by using an amount below the upper limit, the remaining unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and the curing properties tend to be good.

[0101] Examples of polybasic acids and / or their anhydrides 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 their anhydrides.

[0102] Preferably, the compounds are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

[0103] The addition reaction of polybasic acids and / or their anhydrides can be carried out using known methods, and the target product can be obtained by continuing the reaction under conditions similar to those for the addition reaction of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxyl group to epoxy resins. The amount of polybasic acid and / or its anhydride component added is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH / g, and more preferably in the range of 20 to 140 mgKOH / g. Setting the value above the lower limit tends to result in good alkali developability, and setting it below the upper limit tends to result in good curing performance.

[0104] During the addition reaction of polybasic acids and / or their anhydrides, polyfunctional alcohols (polyhydric alcohols) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol may be added to introduce a highly branched structure. In this case, there are no particular restrictions on the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol. Upon heating, the polybasic acid and / or its anhydride undergo an addition reaction with any hydroxyl group present in the mixture of the epoxy resin, the reaction product of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the polyfunctional alcohol.

[0105] By using polyhydric alcohols, the molecular weight of (b1) epoxy (meth)acrylate resin can be increased, allowing for the introduction of branching within the molecule, which tends to balance molecular weight and viscosity. Furthermore, the rate of introduction of acidic groups into the molecule can be increased, which tends to facilitate a balance between sensitivity and adhesion.

[0106] Examples of carboxyl group-containing epoxy (meth)acrylate resins include those described above, for example, those described in Korean Published Patent No. 10-2013-0022955.

[0107] The weight-average molecular weight (Mw) of carboxyl group-containing epoxy (meth)acrylate resins, measured by gel permeation chromatography (GPC), is typically 1000 or more, preferably 1500 or more, more preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more, and typically 10000 or less, preferably 8000 or less, and more preferably 7000 or less. For example, 1000 to 10000 is preferred, 1500 to 10000 is more preferred, 1500 to 8000 is even more preferred, 2000 to 8000 is even more preferred, and 2000 to 7000 is particularly preferred. Setting the value above the lower limit tends to suppress excessive solubility in the developer. Setting the value below the upper limit tends to make it easier to achieve good solubility in the developer.

[0108] The acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, even more preferably 40 mg KOH / g or more, even more preferably 50 mg KOH / g or more, and also preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less. For example, 10 mg KOH / g to 200 mg KOH / g is preferred, 20 mg KOH / g to 150 mg KOH / g is more preferred, 40 mg KOH / g to 120 mg KOH / g is even more preferred, and 50 mg KOH / g to 100 mg KOH / g is even more preferred. Setting it above the lower limit tends to provide appropriate developability and solubility. Setting it below the upper limit tends to suppress excessive development and film dissolution.

[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 substructure represented by the following general formula (b1-I) (hereinafter sometimes abbreviated as "(b1-I) epoxy (meth)acrylate resin") and / or an epoxy (meth)acrylate resin having a substructure represented by the following general formula (b1-II) (hereinafter sometimes abbreviated as "(b1-II) epoxy (meth)acrylate resin").

[0110] [ka]

[0111] In formula (b1-I), R 11 R represents a hydrogen atom or a methyl group. 12 represents a divalent hydrocarbon group which may have substituents, 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 of these independently represents a hydrogen atom or a methyl group, and R 14 R represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. 15 and R 16 Each of the following independently represents a divalent aliphatic group which may have substituents, m and n independently represent integers from 0 to 2, and * represents a bond.

[0114] <(b1-I) Epoxy (meth)acrylate resin> First, we will describe in detail the epoxy (meth)acrylate resin having the substructure represented by the general formula (b1-I).

[0115] [ka]

[0116] In formula (b1-I), R 11 R represents a hydrogen atom or a methyl group. 12 represents a divalent hydrocarbon group which may have substituents, 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 above equation (b1-I), R 12 represents a divalent hydrocarbon group which may have substituents. Examples of divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups.

[0118] Divalent aliphatic groups can be linear, branched, or cyclic. Of these, linear groups are preferred from the viewpoint of developability. On the other hand, cyclic groups are preferred from the viewpoint of reducing the penetration of developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 1 to 10 is still preferred. Setting the number above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0119] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene groups. Among these, the methylene group is preferred from the viewpoint of the rigidity of its skeleton. Examples of divalent branched aliphatic groups include structures in which a divalent linear aliphatic group has a side chain consisting of, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group. The number of rings in a 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. Setting the number above the lower limit tends to result in a strong film with good substrate adhesion. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Examples of divalent cyclic aliphatic groups include groups obtained by removing two hydrogen atoms from rings such as cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isobornane, adamantane, cyclododecane, dicyclopentadiene, and dicyclopentane. Among these, groups obtained by removing two hydrogen atoms from dicyclopentadiene, dicyclopentane, and adamantane rings are preferred from the viewpoint of rigidity of the skeleton.

[0120] Substituents that the divalent aliphatic group may have include, for example, alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0121] Furthermore, examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic ring groups. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. For example, 4 to 20 is preferred, 5 to 15 is more preferred, and 6 to 10 is still preferred. Setting the number of carbon atoms above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number of carbon atoms below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0122] The aromatic hydrocarbon ring in a divalent aromatic hydrocarbon ring group may be a monocyclic or fused ring. Examples of aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings, all of which have two free valencies. Furthermore, the aromatic heterocyclic group may be a monocyclic or a fused ring. Examples of aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinoline rings, phenantholidine rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, all of which have two free valencies. Among these, from the viewpoint of patterning properties, a benzene ring or naphthalene ring having two free valencies is preferred, and a benzene ring having two free valencies is more preferred.

[0123] Examples of substituents that the divalent aromatic ring group may have include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. Of these, unsubstituted groups are preferred from the viewpoint of developability and solubility.

[0124] Furthermore, an example of a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is a group formed by linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, 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. Setting the number above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, 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. Setting the number above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0125] Examples of groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by the following formulas (b1-IA) to (b1-IF). Among these, the group represented by the following formula (b1-IA) is preferred from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

[0126] [ka]

[0127] k represents either 1 or 2. From the viewpoint of adhesion and patternability, k is preferably 1, and from the viewpoint of NMP resistance, k is preferably 2. Furthermore, (b1-I) epoxy (meth)acrylate may contain both a substructure with k = 1 and a substructure with k = 2.

[0128] As described above, the benzene ring in formula (b1-I) may be further substituted with any substituent. Examples of substituents include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. The number of substituents is not particularly limited and may be one or two or more. Among these, from the viewpoint of patterning characteristics, non-substituted is preferred.

[0129] Furthermore, from the viewpoint of ease of synthesis, the substructure represented by formula (b1-I) is preferably the substructure represented by the following formula (b1-I-1).

[0130] [ka]

[0131] In formula (b1-I-1), R 11 , R 12 And k are equivalent to those in the above 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] A polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. 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, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferably 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. Preferably, the substituents listed for the benzene ring in formula (b1-I) can be used.

[0134] (b1-I) The substructure represented by formula (b1-I-1) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, R X The one with the hydrogen atom, and R X It is acceptable for compounds containing polybasic acid residues to be present in the mixture.

[0135] Furthermore, the number of substructures represented by formula (b1-I) contained in one molecule of (b1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, preferably 20 or less, and even more preferably 15 or less. Preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 15. Setting the value above the lower limit tends to result in a stronger film and less surface roughness. Setting the value below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0136] (b1-I) The weight-average molecular weight (Mw) of the 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, most preferably 5000 or more, and also preferably 30000 or less, more preferably 20000 or less, even more preferably 10000 or less, and particularly preferably 8000 or less. For example, 1000 to 30000 is preferred, 1500 to 20000 is more preferred, 1500 to 10000 is even more preferred, 1500 to 8000 is even more preferred, 2000 to 8000 is especially preferred, and particularly preferably 2000 to 7000. Setting it above the lower limit tends to result in a good residual film rate of the photosensitive colored composition. Setting the value below the aforementioned upper limit tends to result in better resolution.

[0137] (b1-I) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, even more preferably 40 mg KOH / g or more, even more preferably 50 mg KOH / g or more, particularly preferably 80 mg KOH / g or more, and also preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 130 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less. For example, 10 mg KOH / g to 200 mg KOH / g is preferred, 20 mg KOH / g to 200 mg KOH / g is preferred, 40 mg KOH / g to 150 mg KOH / g is even more preferred, 50 mg KOH / g to 130 mg KOH / g is even more preferred, and particularly preferably 80 mg KOH / g to 100 mg KOH / g or less. Setting the value above the lower limit tends to improve developability and resolution. Setting the value below the upper limit tends to improve the residual film rate of the photosensitive colored composition.

[0138] The following are specific examples of (b1-I) epoxy (meth)acrylate resins. * indicates a bond in the examples.

[0139] [Chem.]]

[0140] [Chem.]]

[0141] [Chem.]]

[0142] [Chem.]]

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

[0144] [Chem.]]

[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, R 15 and R 16 each independently represents an optionally substituted divalent aliphatic group, m and n each independently represent an integer of 0 to 2, and * represents a bonding site.

[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. Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

[0147] The number of rings in the aliphatic ring 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. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Furthermore, the number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, 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, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is particularly preferred. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Examples of aliphatic rings in the aliphatic ring group include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, adamantane rings, and cyclododecane rings. Among these, the adamantane ring is preferred from the viewpoint of residual film rate and resolution of the photosensitive colored composition.

[0148] On the other hand, the number of rings in an 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, and 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. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. 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, particularly preferably 12 or more, 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, 6 to 40 is more preferred, 8 to 30 is even preferred, 10 to 20 is even more preferred, and 12 to 15 is particularly preferred. Setting the number of carbon atoms above the lower limit tends to result in a stronger film and less surface roughness. Setting the number of carbon atoms below the upper limit tends to result in better patterning properties. Examples of aromatic rings in an aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings. Among these, fluorene rings are preferred from the viewpoint of patterning properties.

[0149] Furthermore, the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but examples include a divalent aliphatic group, a divalent aromatic ring group, and a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

[0150] Divalent aliphatic groups can be linear, branched, or cyclic. Of these, linear groups are preferred from the viewpoint of developability, while cyclic groups are preferred from the viewpoint of reducing the penetration of developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 25 or less, more preferably 20 or less, and still preferably 15 or less. For example, 1 to 25 is preferred, 3 to 20 is more preferred, and 6 to 15 is still preferred. Setting the number above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0151] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene groups. Among these, the methylene group is preferred from the viewpoint of the rigidity of its skeleton. Examples of divalent branched aliphatic groups include structures in which a divalent linear aliphatic group has a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, or tert-butyl group as a side chain. The number of rings in a 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. Setting the number above the lower limit tends to result in a strong film with good substrate adhesion. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Examples of divalent cyclic aliphatic groups include groups obtained by removing two hydrogen atoms from the cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Among these, the group obtained by removing two hydrogen atoms from the adamantane ring is preferred from the viewpoint of rigidity of the skeleton.

[0152] Substituents that the divalent aliphatic group may have include, for example, alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0153] Examples of the divalent aromatic ring group include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. For example, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is still more preferable. When the number of carbon atoms is not less than the above lower limit, a strong film tends to be easily obtained, surface roughening is less likely to occur, and adhesion to a substrate tends to be favorable. When the number of carbon atoms is not more than the above upper limit, deterioration of sensitivity and film thickness reduction during development tend to be easily suppressed, and resolution tends to be improved.

[0154] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be either a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring each having two free valences. The aromatic heterocycle in the aromatic heterocyclic group may be either a single ring or a condensed ring. Examples of the aromatic heterocyclic group include a 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, benzoisoxazole ring, benzoisothiazole 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 having two free valences. Among these, from the viewpoint of patterning characteristics, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

[0155] Examples of substituents that the divalent aromatic ring group may have include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. Of these, unsubstituted groups are preferred from the viewpoint of developability and solubility.

[0156] Furthermore, an example of a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is a group formed by linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, 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. Setting the number above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, 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. Setting the number above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0157] Examples of groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by formulas (b1-IA) to (b1-IF). Among these, the group represented by formula (b1-IC) is preferred from the viewpoint of rigidity of the skeleton and hydrophobicity of the film.

[0158] The manner in which the cyclic hydrocarbon group forming the side chain is bonded to these divalent hydrocarbon groups is not particularly limited, but examples include a configuration in which one hydrogen atom of the aliphatic group or aromatic ring group is substituted with the cyclic hydrocarbon group forming the side chain, or a configuration in which one of the carbon atoms of the aliphatic group is included in the cyclic hydrocarbon group forming the side chain.

[0159] (R 15 , R 16 ) In the above general formula (b1-II), R 15 and R 16 Each of these independently represents a divalent aliphatic group which may have substituents.

[0160] Divalent aliphatic groups can be linear, branched, or cyclic. Of these, linear groups are preferred from the viewpoint of developability, while cyclic groups are preferred from the viewpoint of reducing the penetration of developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. For example, 1 to 20 is preferred, 3 to 15 is more preferred, and 6 to 10 is still preferred. Setting the number above the lower limit tends to result in a stronger film, less surface roughness, and better adhesion to the substrate. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0161] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene groups. Among these, the methylene group is preferred from the viewpoint of the rigidity of its skeleton. Examples of divalent branched aliphatic groups include structures in which a divalent linear aliphatic group has a side chain consisting of, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group. The number of rings in a 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. Setting the number above the lower limit tends to result in a strong film with good substrate adhesion. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Examples of divalent cyclic aliphatic groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, adamantane rings, cyclododecane rings, and dicyclopentadiene rings with two hydrogen atoms removed. Among these, from the viewpoint of skeleton rigidity, dicyclopentadiene rings and adamantane rings with two hydrogen atoms removed are preferred.

[0162] Substituents that the divalent aliphatic group may have include, for example, alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0163] (m, n) In the general formula (b1-II) above, m and n each represent an integer between 0 and 2 independently. Setting them above the lower limit tends to result in good patterning suitability and reduced surface roughness, while setting them below the upper limit tends to result in good developability. 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] Furthermore, from the viewpoint of adhesion to the substrate, the substructure represented by the general formula (b1-II) is preferably the substructure represented by the following general formula (b1-II-1).

[0165] [ka]

[0166] In formula (b1-II-1), R 13 , R 15 , R 16 , m and n are equivalent to those in the above formula (b1-II), and R α represents a monovalent cyclic hydrocarbon group which may have substituents, p represents an integer of 1 or more, and * represents a bond. The benzene ring in formula (b1-II-1) may be further substituted with any substituent.

[0167] (R α ) In the above general formula (b1-II-1), R α This represents a monovalent cyclic hydrocarbon group which may have substituents. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

[0168] The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and 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. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to result in better patterning properties. Furthermore, the number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, 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, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is particularly preferred. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to result in better patterning properties. Examples of aliphatic rings in the aliphatic ring group include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, adamantane rings, and cyclododecane rings. Among these, the adamantane ring is preferred from the viewpoint of strong film properties.

[0169] The number of rings in an 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. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to result in better patterning properties. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably 20 or less, and still preferably 15 or less. For example, 4 to 30 is preferred, 5 to 20 is more preferred, and 6 to 15 is still preferred. Setting the number of carbon atoms above the lower limit tends to result in a stronger film and less surface roughness, while setting it below the upper limit tends to result in better patterning properties. Examples of aromatic rings in an aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Among these, fluorene rings are preferred from the viewpoint of developability and solubility.

[0170] Examples of substituents that the cyclic hydrocarbon group may have include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, amyl, and iso-amyl groups; C1-C5 alkoxy groups such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Of these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0171] p represents an integer greater than or equal to 1, preferably 2 or greater, and preferably 3 or less. For example, 1 to 3 is preferred, and 2 to 3 is more preferred. Setting it above the lower limit tends to result in good film hardening and residual film ratio. Setting it below the upper limit tends to result in good developability.

[0172] Among these, from the viewpoint of strong film hardening, R α It is preferable that the group is a monovalent aliphatic ring group, and 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 substituents include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. The number of substituents is not particularly limited and may be one or two or more. Among these, from the viewpoint of patterning characteristics, non-substituted is preferred.

[0174] The following are specific examples of the substructure represented by the above formula (b1-II-1).

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] Furthermore, the substructure represented by the general formula (b1-II) is preferably the substructure represented by the following general formula (b1-II-2) from the viewpoint of the rigidity of the skeleton and membrane hydrophobicity.

[0181] [ka]

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

[0183] (R β ) In the above formula (b1-II-2), R β This represents a divalent cyclic hydrocarbon group which may have substituents. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

[0184] The number of rings in the aliphatic ring 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. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Furthermore, the number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. For example, 4 to 40 is preferred, 6 to 35 is more preferred, and 8 to 30 is even more preferred. Setting the number above the lower limit tends to suppress film roughness during development. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution. Examples of aliphatic rings in the aliphatic ring group include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, adamantane rings, and cyclododecane rings. Among these, the adamantane ring is preferred from the viewpoint of film reduction during development and resolution.

[0185] On the other hand, the number of rings in an 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. Setting the number above the lower limit tends to result in a stronger film and less surface roughness. Setting the number below the upper limit tends to suppress deterioration of sensitivity and film thinning, and tends to improve resolution. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. 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, 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, 6 to 30 is more preferred, 8 to 20 is even more preferred, and 10 to 15 is particularly preferred. Setting the number of carbon atoms above the lower limit tends to result in a stronger film and less surface roughness. Setting the number of carbon atoms below the upper limit tends to suppress deterioration of sensitivity and film thinning, and tends to improve resolution. Examples of aromatic rings in an aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Among these, fluorene rings are preferred from the viewpoint of developability.

[0186] Examples of substituents that the cyclic hydrocarbon group may have include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, amyl, and iso-amyl groups; C1-C5 alkoxy groups such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0187] Among these, from the viewpoint of suppressing film wear and resolution, R β It is preferable that the group is a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. On the other hand, from the perspective of patterning characteristics, R β It is preferable that the ring is 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 substituents include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. The number of substituents is not particularly limited and may be one or two or more. Furthermore, the two benzene rings may be linked via substituents. Examples of substituents in this case include divalent groups such as -O-, -S-, -NH-, and -CH2-. Among these, unsubstituted is preferable from the viewpoint of patterning properties. Furthermore, methyl group substitution is preferable from the viewpoint of reducing film thinning and other issues.

[0189] The following are specific examples of the substructure represented by formula (b1-II-2). In the examples, * indicates a bond.

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] [ka]

[0194] From the viewpoint of coating film residue rate and patterning characteristics, the substructure represented by the above formula (b1-II) is preferably the substructure represented by the following formula (b1-II-3).

[0195] [ka]

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

[0197] A polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid. Furthermore, if another OH group is removed, the R group in other molecules represented by formula (b1-II-3) is... Z It may be shared with R, that is, Z Multiple equations (b1-II-3) may be linked together via this. 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, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

[0198] (b1-II) The substructure represented by formula (b1-II-3) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, R Z The hydrogen atom and R Z It is acceptable for compounds containing polybasic acid residues to be present in the mixture.

[0199] Furthermore, the number of substructures represented by formula (b1-II) contained in one molecule of (b1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 is still preferred. Setting the value above the lower limit tends to result in a stronger film and less surface roughness. Setting the value below the upper limit tends to suppress deterioration of sensitivity and film thinning, and tends to improve resolution.

[0200] (b1-II) The weight-average molecular weight (Mw) of the 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 2000 or more, more preferably 20000 or less, even more preferably 10000 or less, even more preferably 7000 or less, and particularly preferably 5000 or less. For example, 1000 to 30000 is preferred, 1000 to 20000 is more preferred, 1000 to 10000 is even more preferred, even more preferably 2000 to 7000, and particularly preferably 2000 to 5000. Setting it above the lower limit tends to result in good patterning properties. Setting it below the upper limit tends to result in a stronger film and less surface roughness.

[0201] (b1-II) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, even more preferably 40 mg KOH / g or more, even more preferably 60 mg KOH / g or more, particularly preferably 80 mg KOH / g or more, most preferably 100 mg KOH / g or more, and also preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, and even more preferably 120 mg KOH / g or less. For example, 10 mg KOH / g to 200 mg KOH / g is preferred, 20 mg KOH / g to 200 mg KOH / g is more preferred, 40 mg KOH / g to 150 mg KOH / g is even more preferred, 60 mg KOH / g to 150 mg KOH / g is even more preferred, 80 mg KOH / g to 120 mg KOH / g is particularly preferred, and 100 mg KOH / g to 120 mg KOH / g is especially preferred. Setting the value above the lower limit tends to make it easier to obtain a strong film. Setting the value below the upper limit tends to improve developability and resolution.

[0202] Carboxy group-containing epoxy (meth)acrylate resins may be used individually or as a mixture of two or more resins. Furthermore, a portion of the aforementioned carboxyl group-containing epoxy (meth)acrylate resin may be replaced with other binder resins. That is, carboxyl group-containing epoxy (meth)acrylate resin and other binder resins may be used in combination. In this case, (b) the proportion of carboxyl group-containing epoxy (meth)acrylate resin in the alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less.

[0203] Furthermore, as (b) alkali-soluble resin, (b2) acrylic copolymer resin is preferred from the viewpoint of compatibility with pigments, dispersants, etc., and the one described in Japanese Patent Publication No. 2014-137466 can be preferably used.

[0204] Examples of acrylic copolymer resins include copolymers of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b2-1)") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as "unsaturated monomer (b2-2)"). Examples of unsaturated monomers (b2-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl]; mono(meth)acrylates of polymers having a carboxyl 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 individually or in combination of two or more.

[0205] Furthermore, unsaturated monomers (b2-2) include, for example, 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-vinylbenzylglycidyl 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 decane-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of paracumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

[0207] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 Vinyl ethers such as decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane; Examples of macromonomers that have a mono(meth)acryloyl group at the end of the polymer molecular chain include polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, and polysiloxane. These unsaturated monomers (b2-2) can be used individually or in combination of two or more.

[0208] In copolymers of unsaturated monomer (b2-1) and unsaturated monomer (b2-2), the copolymerization ratio of unsaturated monomer (b2-1) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By copolymerizing unsaturated monomer (b2-1) within this range, it is possible to obtain a photosensitive colored composition with excellent alkali developability and storage stability.

[0209] Examples of copolymers of an unsaturated monomer (b2-1) and an unsaturated monomer (b2-2) include those disclosed in Japanese Patent Publication No. 7-140654, Japanese Patent Publication No. 8-259876, Japanese Patent Publication No. 10-31308, Japanese Patent Publication No. 10-300922, Japanese Patent Publication No. 11-174224, Japanese Patent Publication No. 11-258415, Japanese Patent Publication No. 2000-56118, and Japanese Patent Publication No. 2004-101728. Copolymers of unsaturated monomer (b2-1) and unsaturated monomer (b2-2) can be produced by known methods, but their structure, Mw, and Mw / Mn can also be controlled by methods disclosed, for example, in Japanese Patent Publication No. 2003-222717, Japanese Patent Publication No. 2006-259680, and International Publication No. 2007 / 029871.

[0210] In addition, resins described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 may be used.

[0211] <(c) Photopolymerization initiator> (c) Photopolymerization initiators are components that directly absorb light, undergo decomposition or hydrogen abstraction reactions, and generate polymerization-active radicals. Additives such as polymerization accelerators (chain transfer agents) and sensitizing dyes may be added as needed. Examples of photopolymerization initiators include metallocene compounds containing titanocene compounds as described in Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197; hexaarylbiimidazole derivatives as described in Japanese Patent Publication No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives as described in Japanese Patent Publication No. 10-39503; α-aminoalkylphenone derivatives; and oxime ester compounds as described in Japanese Patent Publication No. 2000-80068 and Japanese Patent Publication No. 2006-36750, etc.

[0212] Examples of metallocene compounds 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), and dicyclopentadienyltitanium Examples include mudi(2,6-difluorophenyl-1-yl), dicyclopentadienyltitaniumdi(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl)titaniumbis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl)titaniumbis(2,6-difluorophenyl-1-yl), and dicyclopentadienyltitanium[2,6-di-fluoro-3-(pyro-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-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 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] Oxime ester compounds are particularly effective as photopolymerization initiators in terms of sensitivity and printmaking properties. For example, when using alkali-soluble resins containing phenolic hydroxyl groups, such highly sensitive oxime ester compounds are especially useful. Because oxime ester compounds have structures that absorb ultraviolet light, transmit light energy, and generate radicals, they are highly sensitive even in small amounts, are stable against thermal reactions, and make it possible to obtain highly sensitive photosensitive colored compositions with small amounts.

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

[0219] [ka]

[0220] In the above equation (IV), R 21a This represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group. R 21b represents any substituent containing an aromatic ring. R 22aThis represents an optionally substituted alkanoyl group or an optionally substituted allyloyl group. n represents an integer, either 0 or 1.

[0221] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in the solvent and sensitivity, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, and more preferably 10 or less. For example, specific examples of alkyl groups include methyl group, ethyl group, propyl group, and cyclopentylethyl group. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl groups, or N-acetyl-N-acetoxyamino groups. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0222] R 21a Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but it is preferably 5 or more from the viewpoint of solubility in photosensitive colored compositions. 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 aromatic ring groups include phenyl, naphthyl, pyridyl, and furyl groups. Of these, phenyl or naphthyl groups are preferred from the viewpoint of developability, and phenyl groups are more preferred. Examples of substituents that the aromatic ring group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, alkyl groups, alkoxy groups, and groups formed by linking these substituents. From the viewpoint of developability, alkyl groups, alkoxy groups, and groups formed by linking them are preferred, and linked alkoxy groups are more preferred. Among these, from the perspective of developability, R 21aIt is preferable that the compound is an aromatic ring group which may have substituents, and it is even more preferable that the compound is an aromatic ring group which has linked alkoxy groups as substituents.

[0224] Also, R 21b Examples of these groups include a substituted carbazolyl group, a substituted thioxanthonyl group, and a substituted diphenyl sulfide group. Of these, a substituted carbazolyl group is preferred from the viewpoint of sensitivity. A substituted diphenyl sulfide group is preferred from the viewpoint of electrical reliability.

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

[0226] Also, R 22a The number of carbon atoms in the allyroyl group is not particularly limited, but from the viewpoint of solubility in the solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, and more preferably 10 or less. Examples of allyroyl groups include benzoyl groups and naphthoyl groups. Examples of substituents that the allyroyl group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and alkyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted. Among these, from the perspective of sensitivity, R 22a It is preferably an alkanoyl group which may have substituents, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

[0227] The initiator described in Japanese Patent Publication No. 2016-133574 is also preferably used because it reduces contamination of the liquid crystal layer by colorants.

[0228] The photopolymerization initiator may be used alone or in combination of two or more types. The photopolymerization initiator may, if necessary, be formulated with a sensitizing dye and polymerization accelerator corresponding to the wavelength of the image exposure light source in order to enhance sensitivity. Examples of sensitizing dyes include xanthene dyes described in Japanese Patent Publication No. 4-221958 and Japanese Patent Publication No. 4-219756, heterocyclic coumarin dyes described in Japanese Patent Publication No. 3-239703 and Japanese Patent Publication No. 5-289335, 3-ketocoumarin compounds described in Japanese Patent Publication No. 3-239703 and Japanese Patent Publication No. 5-289335, pyrometene dyes described in Japanese Patent Publication No. 6-19240, Japanese Patent Publication No. 47-2528 and Japanese Patent Publication No. 54-155292, Examples of dyes having a dialkylaminobenzene skeleton described in Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. 60-88005, Japanese Patent Publication No. 59-56403, Japanese Patent Publication No. 2-69, Japanese Patent Publication No. 57-168088, Japanese Patent Publication No. 5-107761, Japanese Patent Publication No. 5-210240, and Japanese Patent Publication No. 4-288818 are examples.

[0229] Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having both an amino group and a phenyl group within the same molecule are more preferred. For example, 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, 2-(p-dimethylaminophenyl Compounds containing a p-dialkylaminophenyl group, such as (p-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, and (p-diethylaminophenyl)pyrimidine, are preferred, and 4,4'-dialkylaminobenzophenone is particularly preferred. Sensitizing dyes may be used individually or in combination of two or more.

[0230] Examples of polymerization accelerators include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds, which will be discussed later. A single polymerization accelerator may be used, or two or more may be used in combination.

[0231] <(d) Ethylene-unsaturated compounds> The photosensitive colored composition of the present invention contains (d) an ethylenically unsaturated compound. The inclusion of (d) an ethylenically unsaturated compound improves sensitivity. The ethylenically unsaturated compounds used in the present invention are compounds having at least one ethylenically unsaturated group in their molecule. Specifically, examples include (meth)acrylic acid, alkyl (meth)acrylate 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 ethylenic unsaturated groups in one molecule. The number of ethylenic 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 fewer, and more preferably seven or fewer. 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. Setting the number above the lower limit tends to result in high sensitivity. Setting the number below the upper limit tends to improve solubility in the solvent. Examples of polyfunctional ethylenic monomers include, for example, 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 with unsaturated carboxylic acids include acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters obtained by replacing these acrylates with methacrylate; itaconic acid esters obtained by replacing itaconate; crotonic acid esters obtained by replacing cronate; and maleic acid esters obtained by replacing maleate.

[0234] Examples of esters of aromatic polyhydroxy compounds with 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] Esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyvalent hydroxy compounds are not necessarily single compounds, but examples include condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

[0236] Other useful polyfunctional ethylenic monomers used 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 addition products of a polyvalent epoxy compound with hydroxy(meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

[0237] Examples of urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), 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, (d) alkyl ester (meth)acrylate is preferred as the ethylenically unsaturated compound, and dipentaerythritol hexaacrylate is more preferred. These may be used individually or in combination of two or more types.

[0239] <(e) Solvents> The photosensitive coloring composition of the present invention contains (e) a solvent. The inclusion of (e) a solvent allows (a) a colorant to be dispersed or dissolved in the solvent, and also facilitates application. The photosensitive colored composition of the present invention is typically used in a state in which (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and other various materials used as needed, are dissolved or dispersed in a solvent. Among solvents, organic solvents are preferred from the viewpoint of dispersibility and coating properties.

[0240] Among organic solvents, those with a boiling point of 100 to 300°C are preferred from the viewpoint of coating properties, and those with a boiling point of 120 to 280°C are more preferred. Note that the boiling point referred to here is the boiling point at a pressure of 1013.25 hPa, and the same applies to all subsequent boiling point references.

[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, methylhexyl ketone, methyl nonyl ketone, and methoxymethylpentanone; 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-like 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; Examples include 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 ("Cerosolve" is a registered trademark; the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and Digrime (all trade names). These organic solvents may be used individually or in combination of two or more.

[0246] When forming colored spacers using photolithography, it is preferable to select an organic solvent with a boiling point of 100 to 200°C, and more preferably one with a boiling point of 120 to 170°C.

[0247] Among the above organic solvents, glycol alkyl ether acetates are preferred because they offer a good balance of applicability and surface tension, and the solubility of the constituent components in the composition is relatively high. Furthermore, glycol alkyl ether acetates may be used alone, or in combination with other organic solvents. Among the organic solvents to be used in combination, glycol monoalkyl ethers are particularly preferred. In particular, propylene glycol monomethyl ether is preferred due to its solubility of the components in the composition. However, glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability of the resulting photosensitive colored composition tends to decrease, such as an increase in viscosity. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% to 30% by mass, and more preferably 5% to 20% by mass.

[0248] Furthermore, it is also preferable to use an organic solvent with a boiling point of 150°C or higher (hereinafter sometimes referred to as "high-boiling point solvent"). By using such a high-boiling point solvent, the photosensitive colored composition will dry more slowly, but it has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. In other words, it has the effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of colorants, etc., at the tip of the slit nozzle, for example. Due to the high effectiveness of this effect, among the various solvents mentioned above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred.

[0249] When a high-boiling point solvent is used in combination, the content of the high-boiling point solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. Setting it above the lower limit tends to suppress the precipitation and solidification of colorants, etc., at the tip of the slit nozzle, which can cause foreign matter defects. Setting it below the upper limit tends to suppress the slow drying temperature of the composition, which can suppress problems such as poor cycle times in the vacuum drying process and pin marks from pre-baking.

[0250] Furthermore, the high-boiling-point solvent with 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 include a high-boiling-point solvent with a boiling point of 150°C or higher. Preferred high-boiling point solvents include, among the various solvents mentioned above, 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 colored composition of the present invention contains (f) a dispersant. By containing (f) a dispersant, (a) the colorant can be stably dispersed. The (f) dispersant in the photosensitive colored composition of the present invention contains a dispersant (f1) having repeating units represented by the following general formula (1) (hereinafter sometimes referred to as "dispersant (f1)").

[0252] [ka]

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

[0254] [ka]

[0255] (In formula (2), R 5 (This is an alkyl group which may have substituents.)

[0256] The dispersant (f1) is a dispersant having an ammonium group and an alkyl sulfonate ion counteranion. The alkyl sulfonate ion is stably bonded to the ammonium group as an ester-derived anion. Therefore, even when immersed in an amine solvent such as N-methylpyrrolidone (NMP), the dispersant is unlikely to be released from the colorant and remains stable. It is presumed that the dispersant remains adsorbed and covering the surface of the colorant, and that less of the colorant elutes as an impurity.

[0257] On the other hand, since the counter anion of general formula (2) is stably bonded to the ammonium group as an ester-derived sulfonate ion, even if excess dispersant that is not adsorbed on the pigment remains in the cured product, it is unlikely to be released into the liquid crystal as a sulfonate ion. Therefore, it is thought that the voltage retention rate will not decrease as it will have less impact on the orientation of the liquid crystal. In particular, it is estimated that it will not be released easily even after UV irradiation, and the voltage retention rate will not decrease easily.

[0258] (R 1 ~R 3 ) In the above equation (1), R 1 ~R 3 Each of these is independently an optionally substituted alkyl group or an optionally substituted aryl group. R1 ~R 3 Examples of alkyl groups in this context include linear, branched, or cyclic alkyl groups, with linear groups being preferred from the viewpoint of voltage retention rate 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. Keeping it below the above upper limit tends to improve the long-term stability of the dispersion. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. From the viewpoint of the long-term stability of the dispersion, methyl and ethyl groups are preferred, and methyl groups are more preferred. Examples of substituents that alkyl groups may have include alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; aralkyl groups such as benzyl and phenethyl groups; and aryl groups such as phenyl and naphthyl groups. From the viewpoint of dispersibility, it is preferable that alkyl groups be unsubstituted.

[0259] R 1 ~R 3 Examples of aryl groups in this context include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic ring groups. 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 6 or more. Keeping it below the aforementioned upper limit tends to improve dispersibility. Examples of aryl groups include phenyl, naphthyl, and anthracenyl groups. From the viewpoint of dispersibility, phenyl and naphthyl groups are preferred, and phenyl groups are more preferred. Examples of substituents that the aryl group may have include alkyl groups such as methyl and ethyl groups; alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; and aralkyl groups such as benzyl and phenethyl groups. From the viewpoint of dispersibility, it is preferable that the group be unsubstituted.

[0260] In the above equation (1), R 1 ~R 3Two or more of these may bond to each other to form a cyclic structure. Examples of cyclic structures include 5-7 membered nitrogen-containing heterocyclic monocyclic rings or fused rings formed by the fusion of two such rings. Nitrogen-containing heterocyclic rings are preferably non-aromatic, and saturated rings are more preferable. Specifically, the following are examples.

[0261] [ka]

[0262] (In the above formula, R is R 1 ~R 3 It is one of the following. Furthermore, these cyclic structures may have substituents. (* represents a bond.)

[0263] Among these, R 1 ~R 3 Each of these groups is preferably an alkyl group which may have substituents, more preferably an unsubstituted alkyl group, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0264] (X) In equation (1) above, X is a divalent linking group. Examples of divalent linking groups include single bonds, alkylene groups with 1 to 10 carbon atoms, arylene groups with 6 to 12 carbon atoms, and -CONH-R 6 -GROUP, -COOR 7 -Base (however, R 6 and R 7 These can be any single bond, a C1-C10 alkylene group, or a C2-C10 ether group (alkyloxyalkyl group), and from the viewpoint of dispersibility, -COOR 7 -Base is preferred. 7 Among these, from the viewpoint of the long-term stability 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 above equation (1), Y - This is the pair anion represented by the following general formula (2).

[0266] [ka]

[0267] (In formula (2), R 5 (This is an alkyl group which may have substituents.)

[0268] (R 5 ) R 5 Examples of alkyl groups in this context include linear, branched, or cyclic alkyl groups, with linear groups being preferred from the viewpoint of voltage retention rate after UV irradiation. The number of carbon atoms in the alkyl group is not particularly limited, but it is preferably 6 or less, more preferably 4 or less, even more preferably 2 or less, and usually 1 or more. Keeping it below the above upper limit tends to increase the voltage retention rate after UV irradiation. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, and from the viewpoint of voltage retention rate after UV irradiation, methyl and ethyl groups are preferred, with methyl groups being more preferred. Examples of substituents that alkyl groups may have include alkoxy groups such as methoxy and ethoxy groups; and halogen atoms such as fluorine, chlorine, and bromine atoms. From the viewpoint of voltage retention after ultraviolet irradiation, it is preferable that the alkyl group be unsubstituted. Among these, R 5 It is preferable that the alkyl group is unsubstituted, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0269] The dispersant (f1) has repeating units represented by the general formula (1) above, but may also have other repeating units. The dispersant (f1) preferably has repeating units represented by the following general formula (3) from the viewpoint of voltage retention rate before and after UV irradiation.

[0270] [ka]

[0271] (In formula (3), R 8 and R 9 Each of these is independently an optionally substituted alkyl group or an optionally substituted aryl group. 8 and R 9 These may combine with each other to form a ring structure. R 10 This is either a hydrogen atom or a methyl group. Z is a divalent linking group.

[0272] In equation (3) above, R 8 and R 9 Each of these is independently an optionally substituted alkyl group or an optionally substituted aryl group. The optionally substituted alkyl group and optionally substituted aryl group are as follows: R in formula (1) above. 1 ~R 3 The items listed above can be preferably adopted.

[0273] In equation (3) above, R 8 and R 9 These may bond to each other to form a cyclic structure. Examples of cyclic structures include nitrogen-containing heterocyclic monocyclic rings with 5 to 7 members, or fused rings formed by the fusion of two such rings. Nitrogen-containing heterocyclic rings are preferably non-aromatic, and saturated rings are more preferable. Specifically, the following are examples.

[0274] [ka]

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

[0276] In formula (3) above, Z is a divalent linking group. Preferably, the divalent linking group is one of those listed as X in formula (1) above.

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

[0278] [ka]

[0279] (In formula (4), R 11 This is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. R 12 (This is either a hydrogen atom or a methyl group.)

[0280] (R 11 ) R 11 Examples of alkyl groups in this context include linear, branched, or cyclic alkyl groups. From the viewpoint of compatibility with solvents and alkali-soluble resins, linear groups are preferred, and from the viewpoint of affinity for pigments, branched groups are 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, preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. Setting it above the lower limit tends to increase affinity to pigments. Setting it below the upper limit tends to increase compatibility with solvents and alkali-soluble resins and improve dispersibility. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups. From the viewpoint of compatibility with solvents and alkali-soluble resins, methyl and ethyl groups are preferred, with methyl groups being more preferred. Examples of substituents that the alkyl group may have include alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; and aryl groups such as phenyl and naphthyl groups. From the viewpoint of compatibility with solvents and alkali-soluble resins, it is preferable that the alkyl group be unsubstituted, and from the viewpoint of affinity for pigments, it is preferable that it be a phenyl group.

[0281] R 11 Examples of aryl groups in this context include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic ring groups. The number of carbon atoms in the aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. Keeping it below the above upper limit tends to increase the affinity to the pigment. Examples of aryl groups include phenyl, naphthyl, and anthracenyl groups, and from the viewpoint of dispersibility, phenyl and naphthyl groups are preferred, with phenyl being more preferred. Examples of substituents that the aryl group may have include alkyl groups such as methyl and ethyl groups; alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; aryl groups such as phenyl and naphthyl groups; and aralkyl groups such as benzyl and phenethyl groups. From the viewpoint of dispersibility, it is preferable that the group be unsubstituted.

[0282] Among these, R 11 Preferably, the alkyl group may have substituents, more preferably an unsubstituted alkyl group, and even more preferably a methyl group, a butyl group, or an ethylhexyl group.

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

[0284] [ka]

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

[0286] R 13 The group is a methylene group, an ethylene group, or a propylene group, but an ethylene group is preferred from the viewpoint of compatibility with solvents and alkali-soluble resins. R 14 The group is a methyl group, an ethyl group, or a propyl group, but 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 between 1 and 20, but is preferably 1 or greater, more preferably 2 or greater, preferably 10 or less, and 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. Setting the value above the lower limit tends to improve compatibility with solvents and alkali-soluble resins. Setting the value below the upper limit tends to increase affinity with pigments and improve dispersibility.

[0288] The content ratio of the repeating unit represented by the general formula (1) in the dispersant (f1) (hereinafter sometimes referred to as "repeating unit (1)") is not particularly limited, but it 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, particularly preferably 12 mol% or more, and also 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, 5 mol% to 40 mol% is preferred, 7 mol% to 30 mol% is even preferred, even more preferably 7 mol% to 20 mol% is even preferred, and 7 mol% to 15 mol% is particularly preferred. Setting it above the lower limit tends to improve the temporal stability of the dispersion, and setting it below the upper limit tends to improve the dispersibility.

[0289] When the dispersant (f1) contains repeating units represented by the general formula (3) (hereinafter sometimes referred to as "repeating units (3)"), the content ratio is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 12 mol% or more, particularly preferably 15 mol% or more, and 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, 5 mol% to 50 mol% is preferred, 10 mol% to 40 mol% is preferred, 12 mol% to 30 mol% is even more preferred, and 15 mol% to 20 mol% is particularly preferred. Setting the value above the lower limit tends to result in good dispersibility. Setting the value below the upper limit tends to result in good stability of the dispersion over time.

[0290] When the dispersant (f1) contains repeating units (3), the ratio of repeating units (1) to the total of repeating units (1) and repeating units (3) is usually 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 also usually 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, 5 mol% to 100 mol% is preferred, 10 mol% to 80 mol% is more preferred, 20 mol% to 60 mol% is even more preferred, 25 mol% to 50 mol% is even more preferred, and 30 mol% to 40 mol% is particularly preferred. Setting it above the lower limit tends to result in good voltage retention rate and NMP resistance after UV irradiation. Setting it below the upper limit tends to result in good temporal stability of the dispersion.

[0291] When the dispersant (f1) contains repeating units represented by the general formula (4) (hereinafter sometimes referred to as "repeating units (4)"), the proportion of repeating units is not particularly limited, but it 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, particularly preferably 60 mol% or more, and also 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, 30 mol% to 90 mol% is preferred, 40 mol% to 80 mol% is even preferred, 50 mol% to 80 mol% is even more preferred, and 60 mol% to 80 mol% is particularly preferred. Setting it above the lower limit tends to increase affinity to pigments. Setting it below the upper limit tends to increase compatibility with solvents and alkali-soluble resins.

[0292] When the dispersant (f1) contains repeating units represented by the general formula (5) (hereinafter sometimes referred to as "repeating units (5)"), the content ratio is not particularly limited, but it is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 3 mol% or more, and 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. For example, 1 mol% to 30 mol% is preferred, 1 mol% to 20 mol% is preferred, even more preferably 2 mol% to 15 mol% is preferred, even more preferably 2 mol% to 10 mol% is preferred, and particularly preferably 3 mol% to 5 mol%. Setting it above the lower limit tends to increase compatibility with solvents and alkali-soluble resins. Setting it below the upper limit tends to increase affinity with pigments.

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

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

[0295] If the dispersant (f1) has repeating units (4) or repeating units (5), they may be contained in block A, and may be contained in either random copolymerization or block copolymerization. In addition, there may be two or more types of repeating units (4) and repeating units (5) contained in block A, in which case each repeating unit may be contained in block A in either random copolymerization or block copolymerization.

[0296] Repeating units other than repeating units (4) and (5) may be contained in block A, and such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylate chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonic acid ether; and repeating units derived from N-methacryloylmorpholine.

[0297] The amine value of the dispersant (f1) is not particularly limited, but is preferably 20 mg KOH / g or higher, more preferably 30 mg KOH / g or higher, even more preferably 40 mg KOH / g or higher, particularly preferably 45 mg KOH / g or higher, and also preferably 150 mg KOH / g or lower, more preferably 100 mg KOH / g or lower, even more preferably 80 mg KOH / g or lower, and particularly preferably 60 mg KOH / g or lower. For example, 20 mg KOH / g to 150 mg KOH / g is preferred, 30 mg KOH / g to 100 mg KOH / g is more preferred, 40 mg KOH / g to 80 mg KOH / g is even more preferred, and 45 mg KOH / g to 60 mg KOH / g is particularly preferred. Setting it above the lower limit tends to improve dispersibility. Setting it below the upper limit tends to improve the temporal stability of the dispersion. The amine value is expressed as the amount of base and the mass of equivalent KOH per gram 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 mg KOH / g or less, more preferably 5 mg KOH / g or less, even more preferably 1 mg KOH / g, and particularly preferably 0 mg KOH / g.

[0299] The weight-average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, even more preferably 7000 or more, and also preferably 100000 or less, more preferably 50000 or less, and even more preferably 10000 or less. For example, 3000 to 100000 is preferred, 5000 to 50000 is more preferred, and 7000 to 10000 is even more preferred. Setting it above the lower limit tends to improve dispersibility. Setting it below the upper limit tends to improve the temporal stability of the dispersion. Furthermore, in the dispersant of the present invention, the additional anion Y - The presence of may prevent the weight-average molecular weight from being measured properly, in which case Y - Sometimes, the theoretical molecular weight calculated from the weight-average molecular weight before the addition of the marker is used. The theoretical molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, even more preferably 7000 or more, and also preferably 100000 or less, more preferably 50000 or less, and even more preferably 10000 or less. For example, 3000 to 100000 is preferred, 5000 to 50000 is more preferred, and 7000 to 10000 is even more preferred. Setting it above the lower limit tends to improve dispersibility. Setting it below the upper limit tends to improve the temporal stability of the dispersion.

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

[0301] [ka]

[0302] (In formula (2'), R 5 This is equivalent to equation (2) above. 50 R in equation (1) above is 1 ~R 3 (This is synonymous with either of the above.)

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

[0304] Other dispersants that offer good dispersion stability include, for example, dispersants having carboxyl groups or their bases; primary, secondary, or tertiary amino groups; quaternary ammonium bases; and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, and pyrazine. Among these, dispersants having basic functional groups, such as primary, secondary, or tertiary amino groups; quaternary ammonium bases; and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, and pyrazine, are more preferred. Furthermore, polymer dispersants are preferred because they allow for dispersion of pigments with only a small amount of dispersant.

[0305] Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of monomers and macromonomers having amino groups, 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 Bic Chemie), Disparon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Azisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).

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

[0308] Other dispersants may be used individually or in combination of two or more.

[0309] <Other ingredients in the photosensitive coloring composition> In addition to the components mentioned above, the photosensitive colored composition of the present invention may appropriately contain additives such as adhesion enhancers like silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors.

[0310] (1) Adhesion enhancer The photosensitive colored composition of the present invention may contain an adhesion enhancer to improve adhesion to the substrate. Preferred adhesion enhancers include silane coupling agents and phosphate group-containing compounds. Silane coupling agents come in various types, including epoxy, (meth)acrylic, and amino types, which can be used individually 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-isocyanatetopropyltriethoxysilane. Epoxysilane silane coupling agents are particularly preferred. As the phosphate group-containing compound, (meth)acryloyl group-containing phosphates are preferred, and those represented by the following general formulas (g1), (g2), or (g3) are preferred.

[0312] [ka]

[0313] In the above general formulas (g1), (g2), and (g3), R 51 l represents a hydrogen atom or a methyl group, l and l' are integers from 1 to 10, and m is 1, 2, or 3. These phosphate-containing compounds may be used individually or in combination of two or more.

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

[0315] Various types of surfactants can be used, such as anionic, cationic, nonionic, and amphoteric surfactants. Among these, nonionic surfactants are preferred because they are less likely to adversely affect various properties, and fluorine-based and silicone-based surfactants are particularly effective in terms of application properties. Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BIC Chemie), KP340 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Nippon Unicar Co., Ltd.), and FC4430 (manufactured by 3M Corporation). One type of surfactant may be used, or two or more types may be used in any combination and ratio.

[0316] (3) Pigment derivatives The photosensitive colored composition of the present invention may contain a pigment derivative as a dispersion aid to improve dispersibility and shelf life. Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolon, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine derivatives, but phthalocyanine and quinophthalone derivatives are preferred among them. Examples of substituents for pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups, which are directly bonded to the pigment skeleton or via alkyl groups, aryl groups, heterocyclic groups, etc., with sulfonic acid groups being preferred. Furthermore, multiple substituents may be present on a single pigment skeleton.

[0317] Examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, quinophthalone, anthraquinone, quinacridone, diketopyrrolopyrrole, and dioxazine. These may be used individually or in combination of two or more.

[0318] (4) Photoacid generator A photoacid generator is a compound that can generate acid when exposed to ultraviolet light. The acid generated during exposure, in the presence of a crosslinking agent such as a melamine compound, promotes a crosslinking reaction. Among photoacid generators, those with high solubility in solvents, particularly in solvents used in photosensitive colored compositions, are preferred. Examples include diaryliodoniums 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; triarylsulfonium chlorides, bromides, or borofluoride salts, hexafluorophosphate salts, hexafluoroarsenate salts, aromatic sulfonates, and tetrakis(pentafluorophenyl)borate salts 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 agents The photosensitive coloring composition of the present invention may further contain a crosslinking agent, for example, a melamine or guanamine-based compound. Examples of these crosslinking agents include melamine or guanamine-based compounds represented by the following general formula (6).

[0320] [ka]

[0321] In formula (6), R 61 -NR 66 R 67 R represents a group or an aryl group having 6 to 12 carbon atoms. 61 ga-NR 66 R 67In the case of the base, R 62 , R 63 , R 64 , R 65 , R 66 and R 67 One of them is -CH2OR 68 Represents the base, R 61 If it is an aryl group with 6 to 12 carbon atoms, then R 62 , R 63 , R 64 and R 65 One of them is -CH2OR 68 Represents the base, R 62 , R 63 , R 64 , R 65 , R 66 and R 67 The remainder are hydrogen or -CH2OR, independently of each other. 68 Represents the base, 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 and naphthyl groups may be substituted with substituents such as alkyl groups, alkoxy groups, or halogen atoms. The number of carbon atoms in the alkyl and alkoxy groups is 1 to 6, respectively. 68 The alkyl group represented is preferably a methyl group or an ethyl group, with a methyl group being more preferred.

[0322] Melamine compounds corresponding to general formula (6), i.e., compounds of general formula (6-1) below, 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 them is an aryl group, then R 62 , R 63 , R 64 and R 65 One of them is -CH2OR 68 Represents the base, R 62 , R 63 , R 64 , R 65 , R 66 and R 67 The remainder are, independently of each other, hydrogen atoms or -CH2OR 68 Represents the base, R 68 represents a hydrogen atom or an alkyl group.

[0325] A guanamine compound corresponding to general formula (6), i.e., R in general formula (6). 61 Compounds in which the compound 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. Examples include 2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl)perhydro-1,3,5-triazine-2-one (commonly known as N-ethyldimethylol triazone) or its dimethyl ether derivative, dimethylol trimethylene urea or its dimethyl ether derivative, 3,5-bis(hydroxymethyl)perhydro-1,3,5-oxadiazine-4-one (commonly known as dimethylol urone) or its dimethyl ether derivative, and tetramethylol glyoxal diurein or its tetramethyl ether derivative.

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

[0328] (6) Mercapto compounds Mercapto compounds can also be added as polymerization accelerators and to improve adhesion to the substrate.

[0329] Examples of mercapto compounds 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 include heterocyclic mercapto compounds such as 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, as well as aliphatic polyfunctional mercapto compounds. These can be used individually or in combination of two or more.

[0330] (7) Polymerization inhibitors The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. It is believed that by including a polymerization inhibitor, the radical polymerization of the layer beneath the coating film can be inhibited, thereby allowing control of the taper angle (the angle between the support and the cured product in the cross-section of the cured product). 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. Polymerization inhibitors can be used individually or in combination of two or more types. (b) When producing an alkali-soluble resin, a polymerization inhibitor may be included 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, the same or a different polymerization inhibitor may be added when producing the photosensitive colored composition.

[0331] When a 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, and more preferably 0.1% by mass or less, relative to the total solid content of the photosensitive coloring composition. For example, 0.0005% to 0.3% by mass is preferred, 0.001% to 0.2% by mass is more preferred, and 0.01% to 0.1% by mass is even more preferred. Setting the value above the lower limit tends to allow control of the shape of the cured product. Setting the value below the upper limit tends to maintain the necessary sensitivity.

[0332] <Percentage of each component in the photosensitive colored composition> The content of (a) the colorant in the photosensitive colored 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, particularly preferably 35% by mass or more, and 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, 5% to 70% by mass is preferred, 10% to 70% by mass is preferred, 20% to 60% by mass is even preferred, even more preferably 20% to 50% by mass, and particularly preferably 20% to 45% by mass. Setting it above the lower limit tends to ensure light shielding properties. Setting it below the upper limit tends to improve patternability.

[0333] When a photosensitive colored composition contains an organic coloring pigment, the proportion of the pigment is not particularly limited, but it is preferably 5% 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, and also preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. For example, 5% to 70% by mass is preferred, 20% to 70% by mass is more preferred, 20% to 60% by mass is even more preferred, and 20% to 50% by mass is particularly preferred. Setting the amount above the lower limit tends to improve light shielding while suppressing the loss of ultraviolet light necessary for curing. Setting the amount below the upper limit tends to improve NMP resistance.

[0334] (a) When the coloring agent 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 (a) it is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, particularly preferably 12% by mass or more, and also preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. For example, 5% by mass to 40% by mass is preferred, 8% by mass to 40% by mass is preferred, 10% by mass to 30% by mass is even more preferred, and 12% by mass to 20% by mass is particularly preferred. Setting it above the lower limit tends to result in a color tone close to black. Setting it below the upper limit tends to result in high sensitivity.

[0335] (a) When the coloring agent 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 (a) it 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 also 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, 50% by mass to 95% by mass is preferred, even more preferably 70% by mass to 92% by mass, and particularly preferably 80% by mass to 90% by mass. Setting it above the lower limit tends to improve light shielding properties. Setting it below the upper limit tends to improve NMP resistance.

[0336] When the photosensitive colored composition contains a black pigment, its content is not particularly limited, but it 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 also preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. For example, 2% to 60% by mass is preferred, 5% to 60% by mass is more preferred, 10% to 50% by mass is even more preferred, and 20% to 40% by mass is particularly preferred. Setting the content above the lower limit tends to improve light shielding properties. Setting the content below the upper limit tends to improve NMP resistance.

[0337] Furthermore, if the photosensitive colored composition contains an organic black pigment, the proportion of the pigment is not particularly limited, but it 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 also preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. For example, 2% to 60% by mass is preferred, 5% to 60% by mass is more preferred, 10% to 50% by mass is even more preferred, and 20% to 40% by mass is particularly preferred. Setting the amount above the lower limit tends to improve light shielding properties. Setting the amount below the upper limit tends to improve NMP resistance.

[0338] (a) If the coloring agent contains an organic black pigment, the proportion of the pigment is not particularly limited, but (a) it 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, and also preferably 100% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. For example, 5% by mass to 100% by mass is preferred, 10% by mass to 100% by mass is preferred, 15% by mass to 80% by mass is even more preferred, and particularly preferably 20% by mass to 70% by mass. Setting it above the lower limit tends to improve light shielding properties. Setting it below the upper limit tends to improve NMP resistance.

[0339] Furthermore, when the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content ratio is not particularly limited, but (a) it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. For example, 5% to 60% by mass is preferred, 10% to 50% by mass is more preferred, and 15% to 40% by mass is even more preferred. Setting it above the lower limit tends to improve light shielding properties. Setting it below the upper limit tends to improve NMP resistance.

[0340] Furthermore, (a) when the coloring agent contains organic coloring pigments and black pigments, the total percentage of these pigments is not particularly limited, but (a) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 100% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less. For example, 5% to 100% by mass is preferred, 10% to 70% by mass is more preferred, and 15% to 50% by mass is even more preferred. Setting the percentage above the lower limit tends to improve light shielding properties. Setting the percentage below the upper limit tends to improve NMP resistance.

[0341] (b) The content of 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, particularly preferably 35% by mass or more, and 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, 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 especially preferred, and 35% by mass to 45% by mass is particularly preferred. Setting it to above the lower limit tends to suppress the decrease in solubility of the unexposed portion in the developer and suppress development defects. By keeping the value below the aforementioned upper limit, it is possible to maintain appropriate sensitivity, suppress dissolution of the exposed area by the developer, and tend to suppress a decrease in the sharpness and adhesion of the pattern.

[0342] (b1) The content of epoxy (meth)acrylate resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less, and even more preferably 30% by mass or less, in the total solid content of the photosensitive colored composition of the present invention. For example, 5% by mass to 50% by mass is preferred, 10% by mass to 50% by mass is more preferred, 15% by mass to 40% by mass is even more preferred, and 20% by mass to 30% by mass is particularly preferred. Setting it above the lower limit tends to ensure solubility of the unexposed portion in the developer. Setting it below the upper limit tends to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developer, and suppress a decrease in the sharpness and adhesion of the pattern.

[0343] (b) The content of (b1) epoxy (meth)acrylate resin contained in the alkali-soluble resin is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and usually 90% by mass or less, preferably 85% by mass or less, 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. Setting it above the lower limit tends to ensure solubility of the unexposed areas in the developer. Setting it below the upper limit tends to maintain appropriate sensitivity, suppress dissolution of the exposed areas by the developer, and suppress a decrease in the sharpness and adhesion of the pattern.

[0344] (c) The content of 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, and 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% to 15% by mass is preferred, 0.5% to 15% by mass is more preferred, 1% to 10% by mass is even more preferred, 2% to 8% by mass is even more preferred, and 3% to 6% by mass is particularly preferred. Setting it above the lower limit tends to suppress a decrease in sensitivity. Setting it below the upper limit tends to suppress a decrease in solubility of the unexposed portion in the developer and suppress development defects.

[0345] (c) When a polymerization accelerator is used together with the photopolymerization initiator, the content ratio 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, in the total solid content of the photosensitive colored composition of the present invention. Furthermore, it is preferable to use the polymerization accelerator in a ratio 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. Setting the content ratio of the polymerization accelerator above the lower limit tends to suppress the decrease in sensitivity to exposure light. Setting it below the upper limit tends to suppress the decrease in solubility of the unexposed portion in the developer and suppress development defects. Furthermore, when a sensitizing dye is used together with a photopolymerization initiator (c), the proportion of the dye is not particularly limited, but from the viewpoint of sensitivity, it is usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, in the total solid content of the photosensitive colored composition.

[0346] (d) The content of the 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, and more preferably 15% by mass or less, in the total solid content of the photosensitive colored composition of the present invention. For example, 1% to 30% by mass is preferred, 5% to 20% by mass is more preferred, and 10% to 15% by mass is even more preferred. Setting it above the lower limit tends to maintain appropriate sensitivity, suppress dissolution of the exposed area by the developer, and suppress a decrease in the sharpness and adhesion of the pattern. Setting it below the upper limit tends to suppress the penetration of the developer into the exposed area, making it easier to obtain a good image.

[0347] Furthermore, the photosensitive coloring composition of the present invention is prepared by using (e) a solvent so that the total solids 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, it is prepared so that the total solids content is 5% to 50% by mass, preferably 10% to 30% by mass, and more preferably 15% to 25% by mass.

[0348] (f) The proportion of the dispersant 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. 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. Setting it above the lower limit tends to make it easier to obtain sufficient dispersibility. Setting it below the upper limit tends to make it possible to maintain the proportion of other components above a certain level, thereby suppressing a decrease in sensitivity, printability, 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. 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. Setting it above the lower limit tends to result in good dispersibility. Setting it below the upper limit tends to result in a higher voltage retention rate after UV irradiation.

[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, even more preferably 80% by mass or more, and usually 100% by mass or less in the dispersant (f). Setting it above the lower limit tends to improve NMP resistance.

[0351] Furthermore, the ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, usually 50 parts by mass or less, and particularly preferably 30 parts by mass or less. For example, 5 to 50 parts by mass is preferred, 10 to 50 parts by mass is more preferred, and 15 to 30 parts by mass is even more preferred. Setting it above the lower limit tends to make it easier to obtain sufficient dispersibility. Setting it below the upper limit tends to suppress the decrease in sensitivity, plate-making properties, etc., due to a relative decrease in the proportion of other components.

[0352] On the other hand, the content ratio of (b) alkali-soluble resin to 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, particularly preferably 250 parts by mass or more, and 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 to 700 parts by mass is preferred, 100 to 700 parts by mass is more preferred, 150 to 500 parts by mass is even more preferred, 200 to 400 parts by mass is even more preferred, and 250 to 300 parts by mass is particularly preferred. Setting the amount above the lower limit tends to result in a proper dissolution and development state without peeling, etc. Setting the amount below the upper limit tends to result in an appropriate dissolution time in the developer.

[0353] When an adhesion enhancer is used, its content is not particularly limited, but is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by mass, of the total solid content of the photosensitive colored composition. Setting it above the lower limit tends to provide a sufficient adhesion-enhancing effect. Setting it below the upper limit tends to suppress a decrease in sensitivity or the presence of residue after development, which can result in defects.

[0354] When surfactants are used, their content is not particularly limited, but is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass, in the total solid content of the photosensitive coloring composition. Setting the content above the lower limit tends to result in smoothness and uniformity of the coated film. Setting the content below the upper limit tends to result in smoothness and uniformity of the coated film, and also tends to suppress deterioration of other properties.

[0355] <Physical properties of photosensitive colored compositions> The photosensitive colored composition of the present invention has an optical density (OD) of 0.5 or more per 1 μm of film thickness of the coating film. More preferably 0.7 or more, even more preferably 1.0 or more, even more preferably 1.3 or more, particularly preferably 1.5 or more, usually 4.0 or less, preferably 3.0 or less, and more preferably 2.0 or less. For example, 0.5 to 4.0 is preferred, 0.7 to 4.0 is more preferred, 1.0 to 3.0 is even more preferred, 1.3 to 3.0 is even more preferred, and 1.5 to 2.0 is particularly preferred. Setting it above the lower limit tends to provide sufficient light shielding. Setting it below the upper limit tends to provide good voltage retention and NMP resistance. The optical density (OD) per 1 μm of film thickness of the coating can be measured using a coating obtained by curing the photosensitive coloring composition of the present invention, and can be measured using a coating obtained by heat curing at 230°C for 20 minutes. Optical density refers to the transmitted optical density, which is expressed by the ISO visual density in the ISO 5-3 standard, based on the spectral sensitivity characteristics of the light-receiving section. Typically, a CIE (International Commission on Illumination) A light source is used as the light source. An example of a measuring instrument that can be used to measure transmitted optical density is the X-Rite 361T(V) from Sakata Inx Engineering Co., Ltd.

[0356] <Method for producing a photosensitive colored composition> The photosensitive colored composition of the present invention is manufactured according to conventional methods. Typically, (a) the coloring agent is preferably dispersed beforehand using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. This dispersion process atomizes (a) the coloring agent, improving the coating characteristics of the resist.

[0357] Dispersion treatment is usually preferably carried out using a system that combines (a) a colorant, (e) a solvent, and (f) a dispersant, as well as (b) some or all of an alkali-soluble resin (hereinafter, the composition obtained by dispersion treatment may be referred to as "pigment dispersion"). In particular, using a polymer dispersant as (f) the dispersant is preferable because it suppresses the thickening of the obtained pigment dispersion and photosensitive colored composition over time, i.e., it provides excellent dispersion stability. Thus, in the process of producing a photosensitive colored composition, it is preferable to produce a pigment dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. The (a) colorants, (e) solvents, and (f) dispersants that can be used in the pigment dispersion are preferably those described as usable in a photosensitive colored composition. Furthermore, the content ratios of each colorant in the pigment dispersion are preferably those described as content ratios in a photosensitive colored composition.

[0358] When a dispersion treatment is performed on a liquid containing all the components to be incorporated into a photosensitive colored composition, the heat generated during the dispersion treatment may cause highly reactive components to denature. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant. When (a) dispersing the colorant with a sand grinder, glass beads or zirconia beads with a particle size of approximately 0.1 to 8 mm are preferably used. The dispersion treatment conditions are typically a temperature of 0°C to 100°C, preferably in the range of room temperature to 80°C. The dispersion time should be adjusted as appropriate, as the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment device. The guideline for dispersion is to control the gloss of the pigment dispersion so that the 20° specular gloss (JIS Z8741) of the photosensitive colored composition is in the range of 50 to 300. If the gloss of the photosensitive colored composition is low, it often means that the dispersion treatment is insufficient and rough pigment (colorant) particles remain, which may result in insufficient developability, adhesion, resolution, etc. If the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be crushed and a large number of ultrafine particles will be generated, which tends to impair the dispersion stability. The particle size of pigments dispersed in a pigment dispersion is typically 0.03 to 0.3 μm, and can be measured by dynamic light scattering.

[0359] Next, the pigment dispersion obtained by the above dispersion process is mixed with the other components contained in the photosensitive colored composition to obtain a homogeneous solution or dispersion. Since fine dust may be mixed into the liquid during the manufacturing process of the photosensitive colored composition, it is desirable to filter the obtained photosensitive colored composition using a filter or the like.

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

[0361] In the pigment dispersion for the image display device of the present invention, (a) the content ratio of the colorant 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 also preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. For example, 30% to 80% by mass is preferred, 50% to 75% by mass is more preferred, and 60% to 70% by mass is even more preferred. Setting it above the lower limit tends to result in good voltage retention rate and NMP resistance after ultraviolet irradiation. Setting it below the upper limit tends to result in good dispersibility.

[0362] In the pigment dispersion for the image display device of the present invention, the content of black pigment 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, particularly preferably 80% by mass or more, and preferably 75% by mass or less, and more preferably 70% by mass or less, in the total solid content. For example, 30% to 80% by mass is preferred, 50% to 75% by mass is more preferred, and 60% to 70% by mass is even more preferred. Setting it above the lower limit tends to result in good voltage retention rate and NMP resistance after ultraviolet irradiation. Setting it below the upper limit tends to result in good dispersibility.

[0363] In the pigment dispersion for the image display device of the present invention, it is desirable from the viewpoint of light-shielding properties when used as a photosensitive coloring composition that the black pigment includes an organic black pigment represented by the above-described structural formula (1). The content of the organic black pigment of structural formula (1) relative to the colorant (a) 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 more preferably 98% by mass or more.

[0364] In the pigment dispersion for the image display device of the present invention, (f) the content of the dispersant 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, particularly preferably 10% by mass or more, and 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, 1% to 35% by mass is preferred, 5% to 30% by mass is more preferred, 8% to 20% by mass is even more preferred, and 10% to 15% by mass is particularly preferred. Setting it above the lower limit tends to result in good dispersibility. Setting it below the upper limit tends to result in good voltage retention rate and NMP resistance after ultraviolet irradiation.

[0365] In the pigment dispersion for the image display device of the present invention, the content ratio 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 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, 5% to 35% by mass is preferred, 5% to 30% by mass is more preferred, 8% to 20% by mass is even more preferred, and 10% to 15% by mass is particularly preferred. Setting it above the lower limit tends to result in good dispersibility. Setting it below the upper limit tends to result in good voltage retention rate and NMP resistance after ultraviolet irradiation.

[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, even more preferably 80% by mass or more, and usually 100% by mass or less in the dispersant (f). Setting it above the lower limit tends to improve NMP resistance.

[0367] Furthermore, the pigment dispersion for the image display device of the present invention is prepared by using (e) a solvent 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 it is prepared to be 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] A cured product of the present invention can be obtained by curing the photosensitive coloring composition 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, a colored spacer using the photosensitive colored composition of the present invention will be described according to its manufacturing method.

[0370] (1) Support The material used as a support for forming colored spacers is not particularly limited as long as it has adequate strength. Transparent substrates are mainly used, but 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, epoxy resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic resins, and various types of glass. Among these, glass and heat-resistant resins are preferred from the viewpoint of heat resistance. In addition, transparent electrodes such as ITO and IZO may be deposited on the surface of the substrate. Besides transparent substrates, it is also possible to form them on TFT arrays.

[0371] To improve surface properties such as adhesion, the support may be subjected to treatments as needed, such as corona discharge treatment, ozone treatment, or thin-film formation of various resins, including silane coupling agents and urethane resins. The thickness of the transparent substrate is typically in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When performing thin film formation treatment with various resins, the film thickness is typically in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

[0372] (2) Colored spacer The photosensitive colored composition of the present invention can be used in the same applications as known photosensitive colored compositions for color filters. However, the case in which it is used as a colored spacer (black photo spacer) will be described below with reference to a specific example of a method for forming a black photo spacer using the photosensitive colored composition of the present invention.

[0373] Typically, a photosensitive coloring composition is supplied to a substrate where a black photospacer is to be placed, either in the form of a film or a pattern, by methods such as coating, and the solvent is dried. Subsequently, a pattern is formed by methods such as photolithography, which involves exposure and development. After that, 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] Method of supplying to the substrate The photosensitive colored composition of the present invention is typically supplied onto a substrate in a dissolved or dispersed state in a solvent. This can be done by conventionally known methods, such as the spinner method, wire bar method, flow coating method, die coating method, roll coating method, or spray coating method. Alternatively, it may be supplied in a patterned manner, for example, by an inkjet method or printing method. Among these, the die coating method is preferable from an overall viewpoint because it significantly reduces the amount of coating solution used, completely eliminates the influence of mist and other contaminants that can occur with the spin coating method, and suppresses the generation of foreign matter.

[0375] The amount of coating applied varies depending on the application, but for example, in the case of black photospacers, the dry film thickness is usually 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 final spacer, is uniform across the entire substrate. If the variation is small, uneven defects that occur in liquid crystal panels can be suppressed.

[0376] When using the photosensitive coloring composition of the present invention to form black photospacers of different heights in a single batch by photolithography, the final formed black photospacers will have different heights.

[0377] Furthermore, known substrates such as glass substrates can be used as the substrate. The substrate surface is preferably flat.

[0378] [2] Drying method Drying after supplying the photosensitive coloring composition onto the substrate is preferably done using a drying method that utilizes a hot plate, an IR oven, or a convection oven. A vacuum drying method, in which drying is performed in a vacuum chamber without increasing the temperature, may 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 in the range of 15 seconds to 5 minutes at a temperature of 40°C to 130°C, and preferably in the range of 30 seconds to 3 minutes at a temperature of 50°C to 110°C, etc., depending on the type of solvent component, the performance of the dryer used, etc.

[0380] [3] Exposure method Exposure is performed by superimposing a negative mask pattern onto the coating film of the photosensitive colored composition and irradiating it with ultraviolet or visible light through this mask pattern. When exposure is performed using an exposure mask, the exposure mask may be placed close to the coating film of the photosensitive colored composition, or the exposure mask may be placed at a distance from the coating film of the photosensitive colored composition and the exposure light projected through the exposure mask may be projected. A scanning exposure method using laser light without a mask pattern may also be used. If necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, exposure may be performed in an oxygen-free 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 multiple openings, with the opening having the highest average light transmittance (fully transparent opening) and an opening with a lower average light transmittance (intermediately transparent opening). This method creates a difference in the residual film rate due to the difference in average light transmittance between the intermediately transparent opening and the fully transparent opening, i.e., the difference in exposure amount. Intermediate transmission openings can be created, for example, by a matrix-like light-shielding pattern having minute polygonal light-shielding units. Alternatively, they can be created by controlling the light transmittance using films of absorbers such as chromium-based, molybdenum-based, tungsten-based, or silicon-based materials.

[0382] The light sources used for the above exposure are not particularly limited. Examples of light sources include lamps 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, as well as lasers such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. Optical filters can also be used when irradiating with light of a specific wavelength.

[0383] The optical filter may be a thin film type in which the light transmittance at the exposure wavelength can be controlled. Examples of materials for such filters include Cr compounds (oxides, nitrides, oxynitrides, fluorides, etc. of Cr), MoSi, Si, W, and Al.

[0384] The exposure dose is typically 1 mJ / cm². 2 Preferably 5 mJ / cm² 2 More preferably 10 mJ / cm² 2 The above is the standard, and the normal value is 300 mJ / cm². 2 Preferably 200 mJ / cm² 2 More preferably, 150 mJ / cm² 2 The following applies: In the proximity exposure method, the distance between the exposure target 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, and more preferably 300 μm or less.

[0385] [4] Development method After the exposure described above, an image pattern can be formed on the substrate by developing with 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 also be mixtures 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 alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate ester salts; and amphoteric surfactants such as alkyl betaines 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. Furthermore, the organic solvents may be used alone or in combination with water or aqueous solutions of alkaline compounds.

[0389] There are no particular restrictions on the development conditions, but typically the development temperature is 10-50°C, preferably 15-45°C, and more preferably 20-40°C. The development method can be, for example, immersion development, spray development, brush development, or ultrasonic development.

[0390] [5] Exposure and heat curing treatment After development, the substrate may be subjected to further exposure using a method similar to the exposure method described above, or to a heat-curing treatment, if necessary. The heat-curing treatment conditions are a temperature of 100°C to 280°C, preferably 150°C to 250°C, and a duration of 5 to 60 minutes.

[0391] The size and shape of the colored spacer of the present invention are appropriately adjusted according to the specifications of the color filter to which it is applied. However, the photosensitive colored composition of the present invention is particularly useful for simultaneously forming black photospacers with different heights for the spacer and subspacer by photolithography. 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 lower than that of the spacer. Furthermore, from the viewpoint of light shielding, the optical density (OD) per 1 μm of the colored spacer of the present invention is preferably 0.7 or higher, more preferably 1.2 or higher, even more preferably 1.5 or higher, particularly preferably 1.8 or higher, usually 4.0 or lower, and preferably 3.0 or lower. 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 later.

[0392] [Bulkhead] The photosensitive colored composition of the present invention can be suitably used to form partitions, particularly partitions for partitioning the organic layer of an organic electroluminescent device. Examples of organic layers used in an organic electroluminescent device include organic layers used as hole injection layers, hole transport layers, or hole transport layers on hole injection layers, as described in Japanese Patent Publication No. 2016-165396.

[0393] A partition wall using the photosensitive colored composition of the present invention will be described according to its manufacturing method.

[0394] (1) Support The support and substrate for forming the partition wall can be the same as those used for forming the colored spacer as described above.

[0395] (2) Bulkhead The following describes a specific example of a method for forming a partition using the photosensitive colored composition of the present invention, in which the composition is used as a partition.

[0396] Typically, a photosensitive coloring composition is supplied to a substrate where partitions are to be formed, either in the form of a film or a pattern, by methods such as coating, and the solvent is dried. Subsequently, a pattern is formed by methods such as photolithography, which involves exposure and development. After that, partitions are formed on the substrate by additional exposure or heat curing treatment as necessary.

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

[0398] The size and shape of the present invention when used as a partition wall are appropriately adjusted according to the specifications of the organic electroluminescent device to which it is applied, but the height of the partition wall formed from the photosensitive colored composition of the present invention is usually about 0.5 to 10 μm. Furthermore, from the viewpoint of light shielding, the optical density (OD) per 1 μm of the partition wall of the present invention is preferably 0.7 or higher, more preferably 1.2 or higher, even more preferably 1.5 or higher, and particularly preferably 1.8 or higher. It is also usually 4.0 or lower, and preferably 3.0 or lower. 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 later.

[0399] [Organic electroluminescent element] The organic electroluminescent element of the present invention comprises a cured product composed of the aforementioned photosensitive colored composition, for example, a partition wall. For example, various organic electroluminescent devices can be manufactured using a substrate having a partition pattern manufactured by the method described above. The method for forming the organic electroluminescent device is not particularly limited, but preferably, after forming a partition pattern on the substrate by the method described above, the organic electroluminescent device is manufactured by forming organic layers such as pixels using a vapor deposition method in which a functional material is sublimated in a vacuum and deposited into the area surrounded by the partitions on the substrate, or by a wet process such as a casting method, spin coating method, or inkjet printing method.

[0400] Examples of organic electroluminescent devices include bottom-emission and top-emission types. In bottom emission type semiconductors, for example, a partition wall is formed on a glass substrate with stacked transparent electrodes, and a hole transport layer, light-emitting layer, electron transport layer, and metal electrode layer are stacked in the opening surrounded by the partition wall. On the other hand, in top emission type semiconductors, for example, a partition wall is formed on a glass substrate with stacked metal electrode layers, and an electron transport layer, light-emitting layer, hole transport layer, and transparent electrode layer are stacked in the opening surrounded by the partition wall. Examples of light-emitting layers include organic electroluminescent layers as described in Japanese Patent Publication No. 2009-146691 and Japanese Patent No. 5734681. Alternatively, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.

[0401] The layer configuration is not limited to this; for example, the hole transport layer and electron transport layer may be stacked in a multilayer configuration 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] Organic electroluminescent elements may be formed with each RGB color separated into different apertures, or two or more colors may be stacked in a single aperture. From the viewpoint of improving reliability, organic electroluminescent elements may be provided with a sealing layer. The sealing layer has the function of preventing moisture in the air from adsorbing onto the organic electroluminescent element and reducing its luminous efficiency. From the viewpoint of improving light extraction efficiency, organic electroluminescent elements may be provided with a low-reflection film at the interface with air. By placing a 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 structures and ultra-multilayer film technologies can be applied to such low-reflection films.

[0403] When using organic electroluminescent elements as pixels in an image display device, it is necessary to prevent light from the light-emitting layer of one pixel from leaking to other pixels. Furthermore, if the electrodes and other components are made of metal, it is necessary to prevent a decrease in image quality due to reflection of ambient light. Therefore, it is preferable to provide light-shielding properties to the partitions that constitute the organic electroluminescent elements. Furthermore, in organic electroluminescent devices, electrodes must be provided on the upper and lower surfaces of the partition wall; therefore, from the viewpoint of insulation, it is preferable for the partition wall to have high resistance and low dielectric constant. For this reason, when using a coloring agent to provide light-shielding properties to the partition wall, it is preferable to use the aforementioned organic pigment which has 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 can be formed on a liquid crystal drive substrate (array substrate) having a colored spacer formed with the photosensitive colored composition of the present invention, and a liquid crystal cell can be formed by bonding it with a counter electrode substrate. Liquid crystal can then be injected into the formed liquid crystal cell to manufacture an image display device such as a liquid crystal display device containing the cured product of the present invention. Furthermore, by placing a colored spacer formed from the photosensitive colored composition of the present invention on the counter electrode substrate side, bonding it with a liquid crystal drive substrate (array substrate) to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell, an image display device such as a liquid crystal display device containing the cured product of the present invention can be manufactured. As described in Japanese Patent Publication No. 2014-215614, the alignment of liquid crystals can be improved by using a specific alignment material and irradiating a liquid crystal cell with ultraviolet light after injecting liquid crystals.

[0405] Examples of image display devices of the present invention include organic EL display devices having partitions containing the cured product of the present invention and organic electroluminescent light-emitting devices. As long as the organic electroluminescent display device includes the organic electroluminescent element described above, there are no particular restrictions on the type or structure of the image display device. For example, it can be assembled using an actively driven organic electroluminescent element according to conventional methods. For example, it can be formed by the method described in "Organic EL Display" (Ohmsha, published August 20, 2004, authored by Shizuka Tokito, Chihaya Adachi, and Hideyuki Murata). For example, an image may be displayed by combining an organic electroluminescent element that emits white light with a color filter, or by combining organic electroluminescent elements with different emission colors such as RGB.

[0406] [illumination] The organic electroluminescent element containing the cured product of the present invention can be used for illumination. There are no particular restrictions on the type or structure of the illumination, and it can be assembled according to conventional methods using the organic electroluminescent element containing the cured product of the present invention. The organic electroluminescent element may be a simple matrix drive type or an active matrix drive type. To ensure the lighting emits white light, organic electroluminescent elements that emit white light may be used. Alternatively, organic electroluminescent elements of different emission colors may be combined and configured so that the colors mix to produce white light, or the mixing ratio may be adjusted to provide a color-tuning function. [Examples]

[0407] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. The components of the pigment dispersions and photosensitive colored compositions used in the following examples and comparative examples, as well as the evaluation methods thereof, are as follows.

[0408] <Alkali-soluble resin-I> 145 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was stirred while purging with nitrogen and the temperature was raised to 120°C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, Hitachi Chemical Co., Ltd.) were added dropwise, followed by the dropwise addition of 8.47 parts by mass of 2,2'-azobis-2-methylbutyronitrile over 3 hours, and the mixture was continued to stir at 90°C for 2 hours. Next, the reaction vessel was purged with air, and 43.2 parts by mass of acrylic acid, 0.7 parts by mass of trisdimethylaminomethylphenol, and 0.12 parts by mass of hydroquinone were added, and the reaction was continued at 100°C for 12 hours. Subsequently, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 100°C for 3.5 hours. The weight-average molecular weight Mw of the obtained alkali-soluble resin-I, as measured by GPC, was 8400, and the acid value was 80 mgKOH / g.

[0409] <Alkali-soluble resin-II> 300 parts by mass of Nippon Kayaku Co., Ltd.'s "XD1000" (polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252), 87 parts by mass of acrylic acid, 0.2 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and 255 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 100°C until the acid value reached 3.0 mg KOH / g. Then, 145 parts by mass of tetrahydrophthalic anhydride was added and the reaction was carried out 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 mg KOH / g.

[0410] <Pigment-I> CI Pigment Blue 60 <Pigment-II> CI Pigment Orange 64 <Pigment-III> CI Pigment Violet 29 <Pigment-IV> BASF's Irgaphor® Black S 0100 CF (having the chemical structure represented by formula (I-1) below)

[0411] [ka]

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

[0413] The percentages of repeating units represented by formulas (a) to (g) below within the total repeating units are as follows: (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%).

[0414] [ka]

[0415] [ka]

[0416] <Dispersant-II> BYK-LPN6919, 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). The amine value is 120 mgKOH / g and the acid value is 1 mgKOH / g or less.

[0417] The proportions of the repeating units of formula (2a) and formula (3a) in the total repeating units are 33.3 mol% and 6.7 mol%, respectively.

[0418] [ka]

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

[0420] [ka]

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

[0422] [ka]

[0423] <Dispersant-V> Dispersant-II was mixed with 2.85 parts by mass (solid content, PGMEA solution) and p-toluenesulfonic acid with 0.41 parts by mass, and the solid content of the stirred mixture was used as dispersant-V. Dispersant-V is presumed to have repeating units of the following formulas (1a-3), (2a), and (3a). The content percentages of the repeating units of formulas (1a-3), (2a), and (3a) within 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 comprising block A containing repeating units with solvent-philic groups and block B containing repeating units with pigment-adsorbing groups. It has repeating units of the following formulas (h) to (n). The amine value is 70 mgKOH / g.

[0426] The percentages of repeating units represented by the following formulas (h) to (n) within the total repeating units are as follows: (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> Dispersant-II was mixed with 2.90 parts by mass (solid content, PGMEA solution) and 0.37 parts by mass of p-methyl toluenesulfonate, and the solid content of the stirred mixture was used as dispersant-VII. Dispersant-VII is presumed to have repeating units of the following formulas (1a-5), (2a), and (3a). The content percentages of the repeating units of formula (1a-4), formula (2a), and formula (3a) within 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-based photopolymerization initiator having the following chemical structure

[0433] [ka]

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

[0435] [ka]

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

[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 using the following procedure. First, the prepared photosensitive colored composition was applied to a glass substrate using a spin coater to a film thickness of 3.0 μm after heat curing. After drying under reduced pressure for 1 minute, it was dried on a hot plate at 90°C for 140 seconds. The resulting coated film was exposed to light without using an exposure mask. The irradiation light source had an intensity of 45 mW / cm² at a wavelength of 365 nm. 2 Using a high-pressure mercury lamp, the exposure dose was 50 mJ / cm². 2 Next, the resist-coated substrate 1 was obtained by heating and curing it in an oven at 230°C for 20 minutes. 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 the illumination source: approximately 2850K (equivalent to CIE standard light source 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. From the optical density (OD value) and film thickness, the optical density (unit OD value) per unit film thickness (1 μm) was calculated. The OD value is a numerical value indicating light-shielding ability, and a larger value indicates higher light-shielding ability.

[0439] <Evaluation of Voltage Retention Rate (VHR) and Ion Density> Each photosensitive coloring composition was applied to an electrode substrate with an ITO film formed on one side, vacuum-dried for 1 minute, and then dried on a hot plate at 90°C for 140 seconds. The resulting coated film was subjected to a high-pressure mercury lamp at a pressure of 50 mJ / cm². 2 , illuminance 45mW / cm 2 Image exposure was performed under the specified exposure conditions. Next, shower development was performed using an approximately 0.05 mass% potassium hydroxide aqueous solution at 25°C with a water pressure of 0.15 MPa at 25°C. Development was then stopped with pure water, and the substrate was rinsed with a water spray. The shower development time was adjusted between 10 and 20 seconds, to be approximately 1.6 times the time required for the unexposed photosensitive colored composition layer to dissolve and be removed (break time). Subsequently, the substrate was heated and cured in an oven at 230°C for 20 minutes to obtain an evaluation electrode substrate. Otherwise, empty cells were created using the method described in International Publication No. 2018 / 151079. Liquid crystal (MLC-6608, manufactured by Merck Japan) was injected into the resulting empty cell, and the surrounding area was sealed with a UV-curing sealant. The liquid crystal cell was then annealed (heated at 105°C for 2.5 hours in a hot air circulation furnace) to complete the liquid crystal cell for measurement.

[0440] A voltage was applied to the produced measurement liquid crystal cell under the conditions of 5 V, 0.6 Hz, and a frame time of 1667 msec, and the voltage holding ratio before ultraviolet irradiation was measured using a "Liquid Crystal Property Evaluation Device Model 6254" manufactured by Toyo Corporation. The voltage holding ratio serves as an index of electrical reliability. A higher voltage holding ratio is more preferable. Then, using the same apparatus, the current when a triangular wave with a frequency of 0.1 Hz and ±3 V was applied to the measurement liquid crystal cell was measured over time, and a waveform of the temporal change in 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 measurement liquid crystal cell was irradiated with 18 J / cm 2 , at an illuminance of 40 mW / cm 2 using a high-pressure mercury lamp for ultraviolet irradiation. Using the measurement liquid crystal cell after the ultraviolet irradiation, the voltage holding ratio after ultraviolet irradiation and the ion density after ultraviolet irradiation were measured by the same procedure as described above.

[0442] <Evaluation of NMP Resistance> Evaluation of N-methylpyrrolidone (NMP) resistance was performed according to the following procedure. First, the prepared photosensitive coloring composition was applied onto an IZO substrate by 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 coating film was exposed without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp having an intensity of 45 mW / cm 2 at a wavelength of 365 nm was used, and the exposure amount was 50 mJ / cm 2Next, using a developer solution consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (Kao Corporation's "A-60"), shower development was performed at 25°C with a water pressure of 0.05 MPa. After that, development was stopped with pure water and washed with a water spray. The shower development time was set to 1.6 times the time it took for the unexposed coating film to dissolve and be removed, which had been measured in advance. After that, the resist-coated substrate 2 was obtained by heating and curing at an oven temperature of 230°C for 20 minutes. Two measurement substrates (2.5 cm × 1.0 cm square) were cut out from the prepared resist-coated substrate 2 and immersed in a 10 mL vial containing 8 mL of NMP. Then, the NMP elution test was performed with the vial containing the measurement substrates while it was standing in an 80°C hot bath for 40 minutes. After standing 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 in 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 as the measurement condition. The sample solution (NMP elution solution) was also measured in a 1 cm square quartz cell. Absorbance is a dimensionless quantity in spectroscopy that indicates how much the light intensity is attenuated when light passes through a certain object, and is defined by the following formula.

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

[0444] Furthermore, when light is incident from the same light source onto the sample solution and the NMP solution alone, the light intensity transmitted through the NMP solution alone can be considered as I0, and the light intensity transmitted through the sample solution can be considered as I. Therefore, (I / I0) in the above equation represents the light transmittance, and absorbance A is the logarithmic expression of the reciprocal of the transmittance. Absorbance A is a notation used when calculating the concentration of substances contained in the sample solution. When absorbance A=0, it indicates a state where no light is absorbed at all (transmittance 100%), and when absorbance A=∞, it indicates a state where no light is transmitted at all (transmittance 0%). In other words, the higher the absorbance, the more resist coating components are leached into the NMP, indicating poor NMP resistance. The spectral area of ​​the measured absorbance was calculated, and NMP resistance was evaluated according to the following criteria. The spectral area of ​​absorbance, which is the evaluation criterion, can be expressed as the sum of the absorbances at each wavelength, and represents the total sum of the leached resist components.

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

[0446] <Preparation of Pigment Dispersions 1-7> The pigments, dispersants, alkali-soluble resins, and solvents listed in Table 1 were mixed in the mass ratios listed in Table 1. This mixture was dispersed using a paint shaker at a temperature of 25-45°C for 3 hours. 0.5 mm diameter zirconia beads were used as beads, added in an amount equal to 2.5 times the mass of the dispersion. After dispersion, the beads and dispersion were separated by filter to prepare pigment dispersions 1-7. Note that the amount of solvent in Table 1 includes the amount of dispersant and solvent derived from alkali-soluble resin. Furthermore, Table 1 shows the results of the viscosity evaluation of the pigment dispersion measured using the method described above.

[0447] [Table 1]

[0448] [Examples 1-4, Comparative Examples 1-6] Each component was added so that the solid content ratio of each component in the total solid content was as shown in Table 2. Then, PGMEA was added so that the total solid content ratio was 22% by mass. The mixture was then stirred and dissolved to prepare the photosensitive colored compositions of Examples 1-4 and Comparative Examples 1-6. The evaluation results of the unit OD value, voltage retention rate (VHR), ion density, and NMP resistance measured by the above method are shown in Table 2.

[0449] [Table 2]

[0450] Table 2 shows that in Comparative Example 4, the photosensitive colored composition had significantly inferior voltage retention rate, ion density, and NMP resistance after UV irradiation because the counterions in the repeating units represented by formula (1) in dispersant-VI were halogen ions, not the counteranions represented by formula (2). On the other hand, in Comparative Example 5, the optical density per unit film thickness was less than 0.5, and all of these were good even without containing the dispersant described in the present application, thus avoiding the problems of the present application. This is presumed to be because Comparative Example 5 had fewer impurities in the pigment and fewer free counteranions in the dispersant. The photosensitive colored composition of Comparative Example 1 showed significantly inferior NMP resistance. The dispersant-III contained in the photosensitive colored composition of Comparative Example 1 has a counteranion of the ammonium group that forms a salt with a phosphonate ion derived from a weak acid. However, because it is derived from a weak acid, it easily reverts back to a phosphonate and amino group. When immersed in an amine-based solvent such as NMP, the dispersant has high compatibility and easily becomes liberated from the colorant. This reduces the amount of dispersant adsorbed and covering the surface of the colorant, and it is presumed that some of the colorant eluted as an impurity.

[0451] On the other hand, in both Comparative Examples 2 and 3, the voltage retention rate was relatively low before UV irradiation, and even lower after UV irradiation. This is presumed to be because the toluenesulfonate anion and benzenesulfonate anion, which are counter anions to the ammonium groups of dispersants IV and V contained in the photosensitive colored compositions of Comparative Examples 2 and 3, are both stable anions derived from strong acids. Therefore, the excess dispersant sulfonate anions that were not adsorbed on the pigment dissolved into the liquid crystal, lowering the voltage retention rate. Furthermore, UV irradiation further increased the number of counter anions released, further lowering the voltage retention rate.

[0452] Furthermore, in the photosensitive colored composition of Comparative Example 6, the voltage retention rate was relatively low before UV irradiation, and even lower after UV irradiation. This is presumed to be because the methyl toluenesulfonate contained in the dispersant-VI in the photosensitive colorant of Comparative Example 6 is easily released, and further released by UV irradiation, dissolving into the liquid crystal and lowering the voltage retention rate.

[0453] On the other hand, the photosensitive colored composition of Example 1 showed good NMP resistance, and both the voltage retention rate before and after UV irradiation were good. This suggests that the counter anion represented by general formula (2) of the dispersant-I contained in the photosensitive colored composition of Example 1 is an ester-derived anion rather than an acid-derived anion, and therefore the ammonium group did not revert to an amino group, resulting in good NMP resistance. Furthermore, since this counter-anion is stably bonded to the ammonium group as an ester-derived anion, even if excess dispersant remains in the cured product, it is unlikely to be released into the liquid crystal as an anion. Therefore, it is presumed that this has less impact on the orientation of the liquid crystal, resulting in good voltage retention both before and after UV irradiation.

[0454] Furthermore, the lower the unit OD, as in the photosensitive colored composition of Example 3, the better the voltage retention rate and NMP resistance. This is presumed to be due to less elution from pigment impurities. Also, as in the photosensitive colored compositions of Examples 2 and 4, good voltage retention rate and NMP resistance were observed even when containing the organic black pigment of structural formula (1).

Claims

1. A pigment dispersion for use in the production of a photosensitive colored composition for forming a colored spacer in a liquid crystal display device, comprising (a) a colorant, (e) a solvent, and (f) a dispersant, The aforementioned (a) coloring agent contains a black pigment, The (e) solvent contains glycol alkyl ether acetates, A pigment dispersion characterized in that the (f) dispersant contains a dispersant (f1) having repeating units represented by the following general formula (1). 【Chemistry 1】 (In formula (1), R 1 ~R 3 Each of these is independently an optionally substituted alkyl group or an optionally substituted aryl group, R 1 ~R 3 Two or more of these may be joined together to form a ring structure. R 4 This is either a hydrogen atom or a methyl group. X is a divalent linking group. Y - (This is the pair anion represented by the following general formula (2).) 【Chemistry 2】 (In formula (2), R 5 (This is an alkyl group which may have substituents.)

2. The pigment dispersion according to claim 1, wherein the black pigment comprises an organic black pigment.

3. The pigment dispersion according to claim 2, wherein the organic black pigment is an organic black pigment comprising at least one selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound represented by the following general formula (1), a salt of the compound represented by the following general formula (1), and a salt of a geometric isomer of the compound represented by the following general formula (1). 【Transformation 3】 (In formula (1), R 11 and R 16 each independently represent a hydrogen atom, CH 3, CF 3, a fluorine atom, or a chlorine atom; R12, R13, R14, R15, R17, R18, R19, and R20 are each independently a hydrogen atom, a halogen atom, R21, COOH, COOR21, COO-, CONH2, CONHR21, CONR21, R22, CN, OH, OR21, COCR21, OOCNH2, OOCNHR21, OOCNR21, R22, NO2, NH2, NHR21, NR21, R22, NHCOR22, NR21, COR22, N=CH2, N=CHR21, N=CR21, R22 , SH, SR 21, SOR 21, SO 2 R 21, SO 3 R 21, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 21, or SO 2 NR 21 R 22; At least one combination selected from the group consisting of R12 and R13, R13 and R14, R14 and R15, R17 and R18, R18 and R19, and R19 and R20 may be directly bonded to each other, or may be bonded to each other by an oxygen atom, a sulfur atom, NH, or an NR21 bridge; R21 and R22 each independently represent 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.

4. The pigment dispersion according to any one of claims 1 to 3, wherein the dispersant (f1) further has repeating units represented by the following general formula (4). 【Chemistry 4】 (In formula (4), R 11 This is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. R 12 is a hydrogen atom or a methyl group.)

5. The pigment dispersion according to any one of claims 1 to 4, wherein the dispersant (f1) further has repeating units represented by the following general formula (5). 【Transformation 5】 (In formula (5), R 13 This is a methylene group, an ethylene group, or a propylene group. R 14 This is a methyl group, an ethyl group, or a propyl group. R 15 This is either a hydrogen atom or a methyl group. n is an integer between 1 and 20.

6. The pigment dispersion 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 pigment dispersion according to any one of claims 1 to 6, wherein the acid value of the dispersant (f1) is 10 mg KOH / g or less.

Images