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

Abstract

To provide a photosensitive coloring composition excellent in electrical reliability after ultraviolet irradiation.SOLUTION: The photosensitive coloring composition contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. A cured coating film of the photosensitive coloring composition has an optical density per 1 μm film thickness of 0.5 or more. The dispersant (f) contains a dispersant which has a specific repeating unit having an ammonium salt structure in a resin side chain.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive coloring composition and the like. A photosensitive coloring composition preferably used for forming colored spacers or the like in a display device. The present invention relates to a cured product obtained by curing a photosensitive coloring composition, and an image display device including the cured product. [Background technology]

[0002] Liquid crystal displays (LCDs) change the alignment of liquid crystal molecules by turning the voltage applied to the liquid crystal on and off. On the other hand, the components that make up the LCD cell are photolithographically Many of them are formed by methods utilizing photosensitive compositions, such as the Raffy method. This photosensitive composition is easy to form fine structures and is easy to process on substrates for large screens. For these reasons, the scope of its application is expected to expand in the future.

[0003] However, the LCD manufactured using the photosensitive composition has the electrical properties of the photosensitive composition itself. In addition, impurities contained in the photosensitive composition may cause the voltage applied to the liquid crystal to not be maintained. This can cause problems such as uneven display. The part closest to the liquid crystal layer in a splay, for example, the gap between two substrates in a liquid crystal panel In order to keep the thickness constant, so-called columnar spacers and photospacers are used. The impact is huge.

[0004] Conventionally, when a spacer without light-shielding properties is used in a TFT-LCD, the spacer is transparent. The passing light could cause the TFTs acting as switching elements to malfunction. In order to prevent this, a method of using a light-shielding spacer (colored spacer) was considered. It is being done.

[0005] In recent years, with the change in panel structure, colored spacers are now printed uniformly by photolithography. For example, Patent Document 1 discloses a method for forming a quaternary pigment by combining an organic pigment having a specific structure with a quaternary pigment. By using a specific dispersant with an ammonium group, it has excellent light blocking properties, dispersibility and plate making properties. It is disclosed that a photosensitive coloring composition having excellent properties and a sufficiently low relative dielectric constant can be obtained. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2015 / 046178 Summary of the Invention [Problem to be solved by the invention]

[0007] Due to recent changes in panel structure, UV irradiation is now performed after the liquid crystal cell is created to improve the liquid crystal alignment. The method of applying ultraviolet light to the colored spacers and other pigments is becoming more widespread. Although some parts tend to decompose and produce impurities, sufficient electrical reliability is maintained even in such cases. It is required that:

[0008] The present inventors have investigated a photosensitive coloring composition containing a dispersant described in Patent Document 1. However, it was found to be difficult to ensure electrical reliability after UV irradiation.

[0009] The present invention has been made in consideration of the above circumstances, and aims to provide a method for improving electrical reliability after ultraviolet irradiation. The object of the present invention is to provide an excellent photosensitive coloring composition. [Means for solving the problem]

[0010] As a result of intensive research by the present inventors, it has been found that the above problems can be solved by using a specific dispersant. Based on this finding, the present invention has been completed. That is, the gist of the present invention is as follows.

[0011] [1] (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, (d) ethylene A photosensitive coloring composition comprising an organic unsaturated compound, (e) a solvent, and (f) a dispersant. , The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more, The (f) dispersant is a dispersant having a repeating unit represented by the following general formula (1): ). A photosensitive coloring composition comprising:

[0012] [ka]

[0013] (In formula (1), R 1 and R 2 each independently represents an alkyl group which may have a substituent, or R is an optionally substituted aryl group. 1 and R 2 are bonded together to form a ring structure You may do so. R 3 is an alkylene group. R 4 is a polycyclic aromatic hydrocarbon group which may have a substituent. R 5 is a hydrogen atom or a methyl group. X is a divalent linking group. Y is a halogen atom.

[0014] [2] R in the above formula (1) 4 The polycyclic aromatic hydrocarbon group in The photosensitive coloring composition according to [1]. [3] The (a) colorant is at least one selected from the group consisting of red pigments and orange pigments. [1] or The photosensitive coloring composition according to [2]. [4] The photosensitive material according to any one of [1] to [3], wherein the (a) colorant contains a black pigment. Sex coloring composition. [5] The content of the (a) colorant in the total solid content is 10 mass% or more, [4] The photosensitive coloring composition according to any one of the above. [6] The amine value of the dispersant (f1) is 30 mgKOH / g or more, 5] The photosensitive coloring composition according to any one of the above.

[0015] [7] The photosensitive coloring composition according to any one of [1] to [6], which is used for forming a colored spacer. Composition. [8] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [7]. [9] An image display device comprising the cured product according to [8].

[0016]

[10] A face mask for an image display device, comprising (a) a colorant, (e) a solvent, and (f) a dispersant. A material dispersion comprising: The (a) colorant contains a black pigment, The (f) dispersant is a dispersant having a repeating unit represented by the following general formula (1): ) . A pigment dispersion for an image display device, comprising:

[0017] [ka]

[0018] (In formula (1), R 1 and R 2each independently represents an alkyl group which may have a substituent, or R is an optionally substituted aryl group. 1 and R 2 are bonded together to form a ring structure You may do so. R 3 is an alkylene group. R 4 is a polycyclic aromatic hydrocarbon group which may have a substituent. R 5 is a hydrogen atom or a methyl group. X is a divalent linking group. Y is a halogen atom.

[0019]

[11] R in the above formula (1) 4 The polycyclic aromatic hydrocarbon group in The pigment dispersion for an image display device according to

[10] ,

[12] The amine value of the dispersant (f1) is 30 mg KOH / g or more.

[10] Or the pigment dispersion liquid for an image display device according to

[11] . Effect of the Invention

[0020] According to the present invention, there is provided a photosensitive coloring composition having excellent electrical reliability after irradiation with ultraviolet rays. can be done. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments. The present invention is not limited to the above, and can be modified and implemented in various ways within the scope of the present invention. In the present invention, "(meth)acrylic" means "acrylic and / or methacrylic". The same applies to "(meth)acrylate" and "(meth)acryloyl". .

[0022] "(Co)polymer" refers to both homopolymers and copolymers. "Acid (anhydride)" and "(anhydrous)...acid" refer to both acids and their anhydrides. In the present invention, the term "acrylic resin" refers to a (meth)acrylic resin. (co)polymers containing acrylic acid, (co)polymers containing (meth)acrylic acid esters having a carboxy group ) polymer.

[0023] In the present invention, the term "monomer" is the opposite to the so-called polymer. The term includes not only monomers in the strict sense, but also dimers, trimers, oligomers, etc. It's the taste. In the present invention, the "total solid content" refers to the total solid content contained in the photosensitive coloring composition or the pigment dispersion liquid. This refers to all components other than the solvent. Even if the components other than the solvent are liquid at room temperature, Ingredients are not included in the solvent but are included in the total solids. In the present invention, the "weight average molecular weight" refers to a molecular weight determined by gel permeation chromatography (GPC). This refers to the weight average molecular weight (Mw) converted into polystyrene equivalent using a polystyrene-based method (Raffin). In the present invention, the "amine value" refers to the amine value calculated based on the effective solid content, unless otherwise specified. This represents the base value, and is expressed as the mass of KOH equivalent to the amount of base per gram of solid content in the dispersant. The measurement method will be described later. On the other hand, "acid value" means a cation value unless otherwise specified. It represents the acid value converted into effective solid content and is calculated by neutralization titration.

[0024] Also, with respect to pigments, "CI" stands for Color Index.

[0025] In this specification, percentages and parts expressed by "mass" are percentages expressed by "weight". It is synonymous with or part.

[0026] [Photosensitive coloring composition] The photosensitive coloring composition of the present invention comprises (a) Coloring agent (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylenically unsaturated compounds (e) Solvent (f) Dispersants As an essential component, it further contains an adhesion improver such as a silane coupling agent, Surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, etc. The above ingredients are usually used in a state where each ingredient is dissolved or dispersed in a solvent. will be done.

[0027] <(a) Colorant> The photosensitive coloring composition of the present invention contains (a) a colorant. and has moderate light absorption, especially when used for forming light-shielding members such as colored spacers. can provide a suitable degree of light blocking. In addition, the photosensitive coloring composition of the present invention has an optical density per 1 μm of the film thickness of the cured coating film (hereinafter (hereinafter, sometimes referred to as "OD per unit film thickness") is 0.5 or more. (a) By containing a colorant and setting the OD per unit film thickness to the lower limit or more, This improves the light-shielding properties of the resulting cured product, particularly the colored spacer.

[0028] OD per unit film thickness is measured by measuring the optical density and film thickness of a coating made by curing a photosensitive coloring composition. The optical density can be calculated by dividing the optical density by the film thickness. However, for example, the conditions described in the Examples below can be adopted. In order to make the OD per unit film thickness equal to or greater than the lower limit, for example, (a) the type of colorant and the total The content in the solid content may be appropriately adjusted.

[0029] The type of colorant (a) that can be used in the photosensitive coloring composition of the present invention is not particularly limited. Of these, from the viewpoint of durability, it is preferable to use a pigment or a dye. It is preferable to use a

[0030] The pigment contained in the (a) colorant may be of one type alone or of two or more types. In particular, it is important to achieve both uniform light blocking in the visible range and OD per unit film thickness. From this viewpoint, it is preferable to use two or more types. (a) The type of pigment that can be used as the colorant is not particularly limited. For example, Here, the organic coloring pigment is a pigment that exhibits a color other than black. Organic pigments include red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments. Examples of such fees include:

[0031] Among pigments, it is believed to suppress absorption of ultraviolet rays and make it easier to control the shape and step. From the viewpoint of light blocking, it is preferable to use an organic coloring pigment. It is preferable that

[0032] The organic coloring pigment may be used alone or in combination of two or more kinds. From the viewpoint of achieving an OD of 0.5 or more per unit film thickness, organic coloring pigments of different colors are used. It is more preferable to use a combination of organic coloring pigments that exhibit a color close to black. It is more preferable to use the above.

[0033] The chemical structure of these organic coloring pigments is not particularly limited, but may be azo-based, phthalocyanine-based, Quinacridone, benzimidazolone, isoindolinone, dioxazine, indole Examples of pigments that can be used include pigment naphthalene and perylene. The terms below, such as "CI Pigment Red 2," are color index numbers. It means 'C.I.'

[0034] Red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 4 7, 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, 5 7:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 8 1, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101 :1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123 , 144, 146, 147, 149, 151, 166, 168, 169, 170, 172 , 173, 174, 175, 176, 177, 178, 179, 181, 184, 185 , 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 235, 236, 237, 238, 239, 242, 243, 245, 247 , 249, 250, 251, 253, 254, 255, 256, 257, 258, 259 , 260, 262, 263, 264, 265, 266, 267, 268, 269, 270 , 271, 272, 273, 274, 275, and 276. From the viewpoint of light blocking and dispersibility, CI Pigment Red 48:1, 122, 1 49, 168, 177, 179, 194, 202, 206, 207, 209, 224, 2 42, 254, more preferably CI Pigment Red 177, 209, 224, 25 CI Pigment Red 17 is one of the most effective pigments for dispersibility and light blocking. It is preferable to use 7, 254, or 272. When the photosensitive coloring composition is cured by ultraviolet light, In this case, it is preferable to use a red pigment having a low ultraviolet absorption rate. From these, it is more preferable to use CI Pigment Red 254 or 272.

[0035] Orange pigments include CI Pigment Orange 1, 2, 5, 13, and 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, 7 Among these, from the viewpoint of dispersibility and light blocking properties, Therefore, it is preferable to use CI Pigment Orange 13, 43, 64, or 72. When the coloring composition is cured by ultraviolet light, the orange pigment has a low ultraviolet absorption rate. From this viewpoint, it is preferable to use CI Pigment Orange 64, 72 It is more preferable to use

[0036] Blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, and 15:1. , 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 2 9, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 6 7, 68, 71, 72, 73, 74, 75, 76, 78, and 79 can be mentioned. Among these, CI Pigment Blue 15, 15:1, 1 5:2, 15:3, 15:4, 15:6, 60, more preferably CI Pigment Blue -15:6 can be cited as an example. In terms of dispersibility and light blocking properties, CI Pigment Blue 15:6, 16, and 60 were used. In the case where the photosensitive coloring composition is cured by ultraviolet light, it is preferable to use a blue pigment such as It is preferable to use a pigment having a low ultraviolet absorption rate. From this viewpoint, CI pigments are preferred. It is more preferable to use Toblue 60.

[0037] Purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3 :1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. From the viewpoint of light-shielding properties, preferred are CI Pigment Violet 19, 23, and 29, and further Of these, CI Pigment Violet 23 is preferred. In terms of dispersibility and light-shielding properties, it is recommended to use CI Pigment Violet 23 and 29. In the case where the photosensitive coloring composition is cured by ultraviolet light, the purple pigment is preferably a ultraviolet ray. It is preferable to use a material with a low linear absorption rate. From this viewpoint, CI pigment bicarbonate is preferred. It is more preferable to use olet 29.

[0038] Green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 1 4, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 Among these, CI Pigment Green 7, 36 can be listed. Yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9 , 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 3 6, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 6 2, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 1 17, 119, 120, 126, 127, 127:1, 128, 129, 133, 134 , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154 , 155, 157, 158, 159, 160, 161, 162, 163, 164, 165 , 166, 167, 168, 169, 170, 172, 173, 174, 175, 176 , 180, 181, 182, 183, 184, 185, 188, 189, 190, 191 , 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 2 00, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably CI pigments Yellow 83, 138, 139, 150, and 180 are examples.

[0039] Among these, red pigments, orange pigments, and blue pigments are the most popular from the viewpoint of light blocking and shape control. It is preferable to use at least one pigment selected from the group consisting of color pigments and purple pigments.

[0040] Among these, from the viewpoint of light blocking and shape control, at least one of the following pigments is recommended. It is preferable that the compound contains at least one type. Red pigment: CI Pigment Red 177, 254, 272 Orange pigment: CI Pigment Orange 43, 64, 72 Blue pigment: CI Pigment Blue 15:6, 60 Purple pigment: CI Pigment Violet 23, 29

[0041] In addition, when two or more organic coloring pigments are used in combination, the combination of organic coloring pigments is Although not particularly limited, from the viewpoint of light-shielding properties, the pigment may be selected from the group consisting of red pigments and orange pigments. At least one pigment selected from the group consisting of blue pigments and purple pigments It is preferable to do so. The color combination is not particularly limited, but from the viewpoint of light blocking, for example, red Combination of color pigments and blue pigments, combination of blue pigments and orange pigments, blue pigments and orange pigments and a purple pigment.

[0042] Black pigments include organic black pigments and inorganic black pigments. Organic black pigments are used to suppress shrinkage and make it easier to control the shape and step. It is preferred. Among organic black pigments, this pigment suppresses the decrease in the voltage holding rate of liquid crystal and also suppresses the absorption of ultraviolet rays. From the viewpoint of making it easier to control the shape and step, The compound (hereinafter sometimes referred to as "compound (1)"), the geometric isomer of the compound, and a salt of a geometric isomer of the compound. An organic black pigment comprising the compound represented by general formula (1) (hereinafter, may be referred to as "an organic black pigment represented by general formula (1)"). ) is preferably used.

[0043] [ka]

[0044] In formula (1), R 11 and R 16 each independently represents a hydrogen atom, CH3, CF3, a fluorine atom, or a salt Represents elementary atoms; R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 each independently represents a hydrogen atom or a halogen atom atom, R 21 , COOH, COOR 21 , COO - , CONH2, CONHR 21 ,CONR 21 R 22 , C.N., O.H., O.R. 21 , COCR 21 , OOCNH2, OOCNHR 21 , OOCNR 21 R 2 2 , NO2, NH2, NHR 21 , N.R. 21 R 22 , N.H.C.O.R. 22 , N.R. 21 COR 22 , N=CH2, N=CHR 21 , N=CR 21 R 22 , S.H., S.R. 21 , SOR 21 , SO2R 21 , SO3R 21 , S.O. 3H, SO3 - , SO2NH2, SO2NHR21 or SO2NR 21 R 22 R 12 and R 13 , R 1 3 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 Selected from the group consisting of At least one of the combinations may be directly bonded to each other or may be bonded to an oxygen atom, a sulfur atom, or , NH or NR 21 may be connected to each other by bridges; R 21 and R 22 are independent 2. C1-12 alkyl groups, C3-12 cycloalkyl groups, C2-12 an alkenyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms Represents a group.

[0045] Compound (1) and the geometric isomers of compound (1) have the following core structure (wherein (Substituents in the formula are omitted), with the trans-trans isomer being presumably the most stable.

[0046] [ka]

[0047] When compound (1) is anionic, its charge can be changed by any known suitable cation, e.g. For example, metal, organic, inorganic or metallo-organic cations, specifically alkali metals, alkaline earth metals , transition metals, primary ammonium, secondary ammonium, trialkylammonium, etc. ammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complexes In addition, it is preferable that the geometric isomer of compound (1) is a salt compensated by the anion In the case where the compound is a carboxylic acid, it is preferably a salt thereof.

[0048] The substituents in the general formula (1) and their definitions tend to have a high shielding rate. Therefore, the following are preferred because the following substituents have no absorption and do not affect the hue of the pigment. Because it is not considered to be the case. R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably a hydrogen atom or a fluorine atom. Preferably, it is a chlorine atom, or a hydrogen atom. R 13 and R 18 are each independently preferably a hydrogen atom, NO2, OCH3, OC2H5, or a bromine atom. chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2 , α-naphthyl, β-naphthyl, SO3H or SO3 - and more preferably a hydrogen atom. Or SO3H, and particularly preferably a hydrogen atom.

[0049] R 11 and R 16 are each independently preferably a hydrogen atom, CH3 or CF3, more preferably or 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 from At least one combination selected from the group consisting of is the same, and more preferably, R11 teeth R 16 is the same as R 12 is R 17 is the same as R 13 is R 18 is the same as R 14 is R 19 Same as One and R 15 is R 20 is equivalent to.

[0050] Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an ethyl group. propyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2- Methylbutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethyl Propyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylphenyl tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group. It is a silyl group.

[0051] Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group and a cyclopropylmethyl group. cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl group, trimethylcyclohexyl group, thujyl group, norbornyl group, bornyl group, noraryl group group, caryl group, menthyl group, norvinyl group, vinyl group, adamantan-1-yl group or a It is a damantane-2-yl group.

[0052] Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group, an allyl group, and a 2-propene-2- yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1,3-butadiene-2- 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-butyl group 2-methyl-3-buten-2-yl group, 3-methyl-2-buten-1 -yl group, 1,4-pentadiene-3-yl group, hexenyl group, octenyl group, nonenyl group a group, a decenyl group or a dodecenyl group.

[0053] Examples of the cycloalkenyl group having 3 to 12 carbon atoms include a 2-cyclobuten-1-yl group, -Cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexene -1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group group, 4(10)-thujein-10-yl group, 2-norbornen-1-yl group, 2,5-no Bornadiene-1-yl group, 7,7-dimethyl-2,4-norcaradiene-3-yl group Or a camphenyl group.

[0054] Examples of the alkynyl group having 2 to 12 carbon atoms include a 1-propyn-3-yl group and a 1-butyne- 4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4 -pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyne-6- yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl 1,3-hexadiyn-5-yl group, 1-pentenyl group, Cutin-8-yl group, 1-nonyn-9-yl group, 1-decyn-10-yl group or 1-dodecyl group It is a syn-12-yl group.

[0055] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0056] The organic black pigment represented by the general formula (1) is preferably represented by the following general formula (2): Compound (hereinafter also referred to as "compound (2)") and a geometric isomer of compound (2) The organic black pigment comprises at least one selected from the group consisting of:

[0057] [ka]

[0058] A specific example of such an organic black pigment is Irgaphor (registered trademark). An example is Black S 0100 CF (manufactured by BASF). This organic black pigment is preferably dispersed using a dispersant, a solvent, and a method described below. In addition, during dispersion, the sulfonic acid derivative of compound (1), particularly the sulfonic acid derivative of compound (2), The presence of phosphate derivatives may improve dispersibility and storage stability, so organic black pigments are preferred. It is preferable to include these sulfonic acid derivatives.

[0059] Examples of organic black pigments other than the organic black pigment represented by the general formula (1) include aniline. Examples include phosphorus black and perylene black.

[0060] On the other hand, from the viewpoint of light blocking properties, it is preferable to use an inorganic black pigment. Inorganic black pigments include carbon black, acetylene black, lamp black, and borax. Examples of black include carbon black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black is preferably used from the viewpoint of light-shielding properties and image characteristics. Examples of carbon black include the following carbon blacks:

[0061] Mitsubishi Chemical: 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, #97 0, #980, #990, #1000, #2200, #2300, #2350, #240 0, #2600, #2650, #3030, #3050, #3150, #3250, #3 400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Degussa: Printex (registered trademark, the same applies below) 3, Printex 3OP, P rintex30, Printex30OP, Printex40, Printex45 , Printex55, Printex60, Printex75, Printex80 , Printex85, Printex90, Printex A, Printex L , Printex G, Printex P, Printex U, Printex V , PrintexG, SpecialBlack550, SpecialBlack35 0, SpecialBlack250, SpecialBlack100, Special lBlack6, SpecialBlack5, SpecialBlack4, Colo r Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, C olor Black FW200, Color Black S160, Color Black S170 Cabot Corporation: Monarch (registered trademark, the same applies below) 120, Monarch 2 80, Monarch460, Monarch800, Monarch880, Mona rch900, Monarch1000, Monarch1100, Monarch13 00, Monarch1400, Monarch4630, REGAL (registered trademark, hereinafter Same.)99, REGAL99R, REGAL415, REGAL415R, REGAL 250, REGAL250R, REGAL330, REGAL400R, REGAL55 R0, REGAL660R, BLACK PEARLS480, PEARLS130, V ULCAN (registered trademark, the same applies below) XC72R, ELFTEX (registered trademark)-8 Biller: RAVEN (registered trademark, the same applies below) 11, RAVEN 14, RAVE N15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN 40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, R AVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAV EN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, R AVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000 , RAVEN5250, RAVEN5750, RAVEN7000

[0062] Carbon black coated with resin may be used. The use of carbon black has the effect of improving adhesion to glass substrates and volume resistivity. Carbon black coated with resin is disclosed, for example, in JP-A-09-71733. In terms of volume resistivity and dielectric constant, the following carbon blacks can be preferably used: Resin-coated carbon black is preferably used.

[0063] Carbon black to be coated with resin should have a total content of Na and Ca of 1 Carbon black is usually produced by dissolving raw materials such as oil and fuel in the process of production. Na and C mixed in from burning oil (or gas), reaction stop water, granulation water, and even reactor materials Ash containing a, K, Mg, Al, Fe, etc. is contained in the order of percent. Of these, Na and Ca are generally contained in amounts of several hundred ppm or more each. By reducing the amount of these, the penetration into the transparent electrode (ITO) and other electrodes is suppressed, and the electrical This tends to prevent short circuits.

[0064] As a method for reducing the content of ash containing these Na and Ca, carbon black is used. The content of these substances is extremely high as raw material oil, fuel oil (or gas) and reaction quench water during production. Carefully select low-strength materials and minimize the amount of alkaline substances added to adjust the structure. Another method is to remove the carbon black from the furnace. One method is to wash with water or hydrochloric acid to dissolve and remove Na and Ca.

[0065] Specifically, carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, and then redispersed in water. When a poorly soluble solvent is added, the carbon black moves to the solvent side and completely separates from the water. Most of the Na and Ca present in the carbon black are dissolved in water or acid and removed. In order to reduce the total amount of a and Ca to less than 100 ppm, the raw materials must be carefully selected and carbon black must be used. In some cases, it is possible to use the rack manufacturing process alone or the water or acid dissolution method alone, but both methods are used together. By doing so, the total amount of Na and Ca can be more easily reduced to 100 ppm or less.

[0066] Resin-coated carbon black is a so-called acidic carbon black with a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, the fine unit Furthermore, the average particle size is 40 nm or less, and dibutyl phthalate is preferable. It is preferable that the DBP absorption is 140 ml / 100 g or less. This tends to result in a coating film with good light-shielding properties. The average particle size means the number average particle size. Photographs were taken at tens of thousands of magnifications using an electron microscope, and the particles in these photographs were A circle is determined by particle image analysis using an image processing device to measure about 2,000 to 3,000 particles. It means the equivalent diameter.

[0067] There is no particular limitation on the method for preparing the resin-coated carbon black. After adjusting the amount of carbon black and resin, 1. Mix resin, cyclohexanone, and toluene. A resin solution made by mixing and dissolving a resin in a solvent such as benzene or xylene and heating it, and carbon black The mixture was stirred and mixed with a suspension of carbon black and water to separate the carbon black from the water. The composition obtained by removing the carboxylic acid and kneading the mixture under heating is formed into a sheet, pulverized, and then dried. Method 2: The resin solution and suspension prepared in the same manner as above were mixed and stirred to obtain carbon black. After the resin is granulated, the resulting granules are separated and heated to remove the remaining solvent and water. 3. A method of dissolving carboxylic acids such as maleic acid and fumaric acid in the above-mentioned solvents. Add carbon black, mix, dry, and remove the solvent to obtain a carboxylic acid-impregnated carbon After obtaining the black, a resin is added to it and dry blended; 4. Resin to be coated The reactive group-containing monomer component constituting the above is mixed with water at high speed to prepare a suspension, which is then polymerized and cooled. After obtaining a reactive group-containing resin from the polymer suspension, carbon black was added to the resin and mixed. The carbon black is kneaded to react with the reactive group (to graft the carbon black), A method of cooling and crushing, etc., can be adopted.

[0068] The type of resin used for the coating process is not particularly limited, but synthetic resins are common. Furthermore, resins with benzene rings in their structure have stronger amphoteric surfactant properties. This is preferable from the standpoint of dispersibility and dispersion stability. Specific synthetic resins include phenol resin, melamine resin, xylene resin, and diallyl resin. Thermosetting resins such as phthalate resins, glyptal resins, epoxy resins, and alkylbenzene resins Grease, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene Polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyparaphenylene phthalamide, polyamideimide, polyimide, polyaminobismaleimide, polya Tersulfopolyphenylenesulfone, polyarylate, polyetheretherketone The amount of resin to be coated on the carbon black is determined by the following formula: The content is preferably 1 to 30% by mass based on the total amount of black and resin, and is set to the lower limit value or more. On the other hand, by making the content equal to or less than the upper limit, This tends to prevent adhesion between resins and improve dispersibility.

[0069] The carbon black thus coated with the resin is then coated with a colored spacer in the usual manner. The color filter having the colored spacer as a component can be used as a light-shielding material for a color filter. The carbon black can be prepared by a conventional method. There is a tendency that colored spacers with high light efficiency and low surface reflectance can be achieved at low cost. By coating the carbon black surface with resin, Ca and Na are absorbed into the carbon black. It is also speculated that it may have a containment function.

[0070] These pigments usually have an average particle size of 1 μm or less, preferably 0.5 μm or less, and more preferably It is preferable to disperse the powder so that the average particle size is 0.05 to 0.25 μm. The measure is the number of pigment particles. In the photosensitive coloring composition of the present invention, the average particle size of the pigment is determined by dynamic light scattering (DLS) The particle size was measured using a sufficiently diluted sensor. Photochromic coloring composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. If there is a concentration recommended by the measuring device, follow that concentration) and measure at 25°C. Determine.

[0071] In the photosensitive coloring composition of the present invention, a colorant such as an organic coloring pigment or a black pigment is used. One type may be used alone, or two or more types may be used in combination. From the viewpoint of easy control, it is preferable to use organic black pigments in combination with organic coloring pigments. On the other hand, from the viewpoint of light-shielding properties, it is preferable to use carbon black and an organic coloring pigment in combination. It is nice.

[0072] In addition to the above-mentioned organic color pigments and black pigments, dyes may also be used. The dyes that can be used are azo dyes, anthraquinone dyes, phthalocyanine dyes, and quinone dyes. imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, etc. Some examples include: Examples of azo dyes include CI Acid Yellow 11 and CI Acid Orange 12. CI Acid Red 7, CI Acid Red 37, CI Acid Red 180, CI Acid Dobleu 29, CI Direct Red 28, CI Direct Red 83, CI . Direct Yellow 12, CI Direct Orange 26, CI Direct Green 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, C. I. Disperse Blue 165, CI Basic Blue 41, CI Basic Red CI Mordant Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Dant Black 7, etc.

[0073] Examples of anthraquinone dyes include CI Bat Blue 4 and CI Acid Blue 5. Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue Examples include CI Disperse Blue 60, etc. In addition, phthalocyanine dyes such as CI Pad Blue 5 are also available. Imine dyes include, for example, CI Basic Blue 3 and CI Basic Blue. 9, etc. are quinoline dyes, for example, CI Solvent Yellow 33, CI A CI Yellow 3, CI Disperse Yellow 64, etc. are nitro dyes. For example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, etc.

[0074] <(b) Alkali-soluble resin> The alkali-soluble resin (b) used in the present invention is a resin containing a carboxyl group or a hydroxyl group. There is no particular limitation as long as the resin is a resin, and examples thereof include epoxy (meth)acrylate resins and acrylic resins. Grease, carboxyl group-containing epoxy resin, carboxyl group-containing urethane resin, novolac resin , polyvinylphenol resins, etc., among which (b1) Epoxy (meth)acrylate resin (b2) Acrylic copolymer resin These are preferably used alone or in combination from the viewpoint of excellent plate making properties. can be used in combination.

[0075] <(b1) Epoxy (meth)acrylate resin> (b1) Epoxy (meth)acrylate resins are made from epoxy compounds (epoxy resins) α,β-Unsaturated monocarboxylic acid and / or α,β- having a carboxy group in the ester moiety The hydroxyl group formed by the reaction with the unsaturated monocarboxylic acid ester is further converted into a polybasic React with a compound having two or more substituents that can react with hydroxyl groups, such as an acid and / or its anhydride. The resin obtained by this process is In addition, before reacting the polybasic acid and / or its anhydride with the hydroxyl group, a reaction with the hydroxyl group is carried out. After reacting a compound having two or more reactive substituents, a polybasic acid and / or its anhydride are added. Resins obtained by reacting such substances are also included in the above (b1) epoxy (meth)acrylate resins. Can be enjoyed.

[0076] Also, a compound having a functional group capable of further reacting with the carboxy group of the resin obtained by the above reaction The resin obtained by reacting the above is also included in the above (b1) epoxy (meth)acrylate resin. can be. In this way, epoxy (meth)acrylate resins essentially contain epoxy groups in their chemical structure. and is not limited to "(meth)acrylate", but is an epoxy compound Since (epoxy resin) is the raw material and "(meth)acrylate" is a typical example, It is named this way according to its use.

[0077] The epoxy (meth)acrylate resin (b1) used in the present invention is particularly the following epoxy resin: Epoxy (meth) acrylate resin (b1-1) and / or epoxy (meth) acrylate Resin (b1-2) (hereinafter referred to as "carboxy group-containing epoxy (meth)acrylate resin") ) is preferably used from the viewpoint of developability and reliability. In addition, as for (b1) epoxy (meth)acrylate resin, from the viewpoint of outgassing, More preferably, a copolymer having an aromatic ring in the main chain can be used.

[0078] <Epoxy (meth)acrylate resin (b1-1)> Epoxy resin is added with α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid having a carboxy group A monobasic acid ester is added to the ester, and then a polybasic acid and / or its anhydride are reacted. An alkali-soluble resin obtained by <Epoxy (meth)acrylate resin (b1-2)> Epoxy resin is added with α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid having a carboxy group A monocarboxylic acid ester is added to the ester, and a polyhydric alcohol and a polybasic acid and / or is an alkali-soluble resin obtained by reacting it with its anhydride.

[0079] Here, epoxy resin includes the raw material compounds before they are thermally cured to form the resin. The epoxy resin is appropriately selected from known epoxy resins. The epoxy resin may be a phenolic compound and an epihalohydrin. The compound obtained by the reaction can be used. or a compound having a divalent or higher phenolic hydroxyl group, whether a monomer or a polymer. good. The types of epoxy resins used as raw materials are cresol novolac epoxy resins, phenanthroline, and phenylene. Nol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin epoxy resin, naphthalene novolac type epoxy resin, dicyclopentadiene and phenol or cresol polyaddition reaction product with epihalohydrin. adamantyl group-containing epoxy resins, fluorene-type epoxy resins, etc. can be preferably used. Thus, those having an aromatic ring in the main chain can be preferably used.

[0080] Specific examples of epoxy resins include bisphenol A type epoxy resins (e.g. For example, Mitsubishi Chemical Corporation's "jER (registered trademark, hereinafter the same) 828" and "jER100 1", "jER1002", "jER1004", etc.), bisphenol A type epoxy resin Epoxy resins (e.g., , Nippon Kayaku's "NER-1302" (epoxy equivalent 323, softening point 76°C), Phenol F-type resin (e.g., Mitsubishi Chemical's "jER807" and "EP-4001 ", "EP-4002", "EP-4004", etc.), bisphenol F type epoxy resin Epoxy resins obtained by reacting alcoholic hydroxyl groups with epichlorohydrin (e.g., Nippon Kayaku's "NER-7406" (epoxy equivalent: 350, softening point: 66°C), bisphenol A phenol S type epoxy resin, biphenyl glycidyl ether (e.g., Mitsubishi Chemical Corporation) "YX-4000" manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type epoxy resin (e.g., "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152" and "EP-154" manufactured by Daikin Industries, Ltd. "DEN-438" manufactured by U.S. Chemical Co., Ltd.), (o,m,p-) cresol novolac type epoxy olefin resin (for example, "EOCN (registered trademark, the same applies below)-102S" manufactured by Nippon Kayaku Co., Ltd., "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (For example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenol methane type ethylene glycol epoxy resin (for example, "EPPN (registered trademark, the same applies below)-501" manufactured by Nippon Kayaku Co., Ltd., "EPPN-502", "EPPN-503"), alicyclic epoxy resin (manufactured by Daicel Corporation "Celloxide (registered trademark, the same applies below) 2021P" and "Celloxide EHPE" Glycidyl epoxy resin obtained by the reaction of dicyclopentadiene with phenol. Resin (e.g., "EXA-7200" manufactured by DIC, "NC-730" manufactured by Nippon Kayaku Co., Ltd.) 0"), epoxy resins represented by the following general formulas (B1) to (B4), etc. are preferably used. Specifically, the epoxy resin represented by the following general formula (B1) is "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (B2): "NC-3000" by Osaka Organic Chemical Industry Co., Ltd., and the epoxy resin represented by the following general formula (B3) "E-201" manufactured by Nippon Steel & Sumitomo Metal Industries, Ltd., and "E-201" manufactured by Nippon Steel & Sumitomo Metal Industries, Ltd., which is an epoxy resin represented by the following general formula (B4). An example is "ESF-300" manufactured by Kin Kagaku Co., Ltd.

[0081] [ka]

[0082] In the above general formula (B1), a is an average value and represents a number from 0 to 10; 111 Each Independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, It represents an alkyl group, a phenyl group, a naphthyl group, or a biphenyl group. Multiple R 111 may be the same or different.

[0083] [ka]

[0084] In the above general formula (B2), b1 and b2 each independently represent an average value and are numbers from 0 to 10. R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, It represents a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. O, multiple R in one molecule 121 may be the same or different.

[0085] [ka]

[0086] In the above general formula (B3), X is represented by the following general formula (B3-1) or (B3-2): The molecular structure contains one or more adamantane structures. Represents.

[0087] [ka]

[0088] In the above general formulae (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 teeth each independently represents an adamantyl group which may have a substituent, a hydrogen atom, represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. , * represents a bond.

[0089] [ka]

[0090] In the above general formula (B4), p and q each independently represent an integer of 0 to 4; 141 and R 142 each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom; R 143 and R 144 each independently represents an alkylene group having 1 to 4 carbon atoms; and each of x and y independently represents an integer of 0 or more. represent.

[0091] Among these, an epoxy resin represented by any one of general formulas (B1) to (B4) is used. It is preferable.

[0092] α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid having a carboxy group Acid esters include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoate. Aromatic acid, (meth)acrylic acid α-position haloalkyl, alkoxyl, halogen, nitro, cyano Monocarboxylic acids such as 2-(meth)acryloyloxyethyl succinic acid, 2-( Meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl phthalate Acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxypropyl succinate, p) Acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyl tetraacetate Hydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid Acryloyloxypropyl maleate, 2-(meth)acryloyloxybutyl succinate, 2- (Meth)acryloyloxybutyl adipate, 2-(meth)acryloyloxybutyl hydride 2-(meth)acryloyloxybutylphthalate, 2-(meth)acryloyloxybutylphthalate, Dibutyl maleate (meth), acrylic acid, ε-caprolactone, β-propiolactone lactones such as γ-butyrolactone, δ-valerolactone, etc. mer, or hydroxyalkyl (meth)acrylate, pentaerythritol tri(meth)acrylate p) Acrylate with acids such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) (Anhydride) addition monomers, (meth)acrylic acid dimers, etc. Among these, (meth)acrylic acid is particularly preferred from the viewpoint of sensitivity.

[0093] Epoxy resin is added with α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid having a carboxy group As a method for adding the monocarboxylic acid ester, a known method can be used. For example, in the presence of an esterification catalyst, α,β-unsaturated monocarboxylic acids are synthesized at temperatures of 50 to 150°C. α,β-unsaturated monocarboxylic acid ester having carboxylic acid or carboxyl group and epoxy resin The esterification catalyst used here is triethylamine. , trimethylamine, benzyldimethylamine, benzyldiethylamine and other tertiary amines , Tetramethylammonium chloride, Tetraethylammonium chloride, Dodecyl For example, a quaternary ammonium salt such as trimethylammonium chloride can be used.

[0094] In addition, epoxy resin, α,β-unsaturated monocarboxylic acid or α,β having a carboxy group - Select one type each of the unsaturated monocarboxylic acid ester and the esterification catalyst. They may be selected and used, or two or more of them may be used in combination. α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid having a carboxy group The amount of the acid ester used is in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. The range is preferably 0.7 to 1.1 equivalents, and more preferably 0.7 to 1.1 equivalents. The amount of carboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is By setting the amount of unsaturated groups to the lower limit or more, it is possible to prevent a shortage in the amount of unsaturated groups introduced. On the other hand, when the amount is less than the upper limit, the reaction with the anhydride tends to be sufficient. By this, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid having a carboxy group is obtained. It is possible to suppress the remaining unreacted carboxylate, which tends to improve the curing properties. is recognized.

[0095] Polybasic acids and / or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, Acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, Benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetra Hydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarbo Examples of the acid include one or more selected from the group consisting of carboxylic acids, carboxylic acids, and anhydrides thereof.

[0096] Preferred 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, biphenyl tetrahydrophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride. be.

[0097] A known method can be used for the addition reaction of the polybasic acid and / or its anhydride. Addition of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid having carboxyl groups to epoxy resin The reaction is continued under the same conditions as the addition reaction of the monocarboxylic acid ester to obtain the desired product. The amount of polybasic acid and / or its anhydride added can be adjusted according to the amount of the resulting carboxyl group-containing copolymer. The acid value of the epoxy (meth)acrylate resin is in the range of 10 to 150 mg KOH / g. It is preferable that the amount of the acid is in the range of 20 to 140 mgKOH / g. By adjusting the amount to be equal to or more than the lower limit, the alkali developability becomes good. By setting the content to be equal to or less than the upper limit, the curing performance tends to be good.

[0098] During the addition reaction of the polybasic acid and / or its anhydride, trimethylolpropane, Ditrimethylolpropane, Pentaerythritol, Dipentaerythritol, Trimethylol Polyfunctional alcohols such as dichloroethane and 1,2,3-propanetriol (polyhydric alcohols) Alternatively, a multi-branched structure may be introduced by adding ruthenium.

[0099] In this case, there is no particular restriction on the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol. By heating, the epoxy resin and the α,β-unsaturated monocarboxylic acid or carboxyl group are bonded to each other. Mixture of the reaction product of α,β-unsaturated monocarboxylic acid ester with polyfunctional alcohol Any hydroxyl groups present in the polymer undergo an addition reaction with a polybasic acid and / or its anhydride.

[0100] By using polyhydric alcohol, (b1) the molecular weight of the epoxy (meth)acrylate resin It is possible to increase the viscosity and introduce branches into the molecule, making it possible to balance the molecular weight and viscosity. In addition, the introduction rate of acid groups into the molecule can be increased, improving sensitivity, adhesion, etc. There is a tendency to achieve a good balance.

[0101] In addition to the above, the carboxyl group-containing epoxy (meth)acrylate resins include: Examples include those described in Korean Patent Publication No. 10-2013-0022955.

[0102] Gel permeation chromatography of carboxyl group-containing epoxy (meth)acrylate resin The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is usually calculated as polystyrene equivalent. 1000 or more, preferably 1500 or more, more preferably 2000 or more, more preferably It is preferably 3000 or more, more preferably 4000 or more, and particularly preferably 5000 or more. It is usually 10,000 or less, preferably 8,000 or less, and more preferably 7,000 or less. By setting the content to the lower limit or more, there is a tendency that the solubility in the developer can be prevented from becoming too high. By setting the content to the upper limit or less, the solubility in the developer tends to be good. do.

[0103] The acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but Preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and more preferably 40 mg KOH / g or more is more preferred, and 50 mg KOH / g or more is even more preferred; , 200 mg KOH / g or less is preferable, 150 mg KOH / g or less is more preferable, It is more preferably 20 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. By setting the value to be equal to or more than the lower limit, there is a tendency that appropriate development solubility can be obtained. By setting the amount to the range below 100%, it is possible to suppress the film from dissolving due to excessive development.

[0104] The chemical structure of the epoxy (meth)acrylate resin is not particularly limited, but it is preferable that the resin has good developability, reliability, and From the viewpoint of compatibility, an epoxy (meth)acrylate having a partial structure represented by the following general formula (b1-I) is Acrylate resin (hereinafter abbreviated as "(b1-I) epoxy (meth)acrylate resin" ) and / or an aryl group having a partial structure represented by the following general formula (b1-II): Epoxy (meth)acrylate resin (hereinafter referred to as "(b1-II) epoxy (meth)acrylate" It is preferable that the resin contains a carboxylic acid-based resin.

[0105] [ka]

[0106] In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 may have a substituent. Formula (b1-I) represents a divalent hydrocarbon group, k represents 1 or 2, and * represents a bond. The benzene ring in may be further substituted with any substituent.

[0107] [ka]

[0108] In formula (b1-II), R 13 each independently represents a hydrogen atom or a methyl group; R 14 is a circular represents a divalent hydrocarbon group having a hydrocarbon group as a side chain, and R 15 and R 16 are each independently represents a divalent aliphatic group which may have a substituent, and m and n each independently represent an integer of 0 to 2. and * represents a bond.

[0109] <(b1-I) Epoxy (meth)acrylate resin> First, an epoxy (meth)acrylate having a partial structure represented by the general formula (b1-I) is The copolymer resin will now be described in detail.

[0110] [ka]

[0111] In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 may have a substituent. Formula (b1-I) represents a divalent hydrocarbon group, k represents 1 or 2, and * represents a bond. The benzene ring in may be further substituted with any substituent.

[0112] (R 12 ) In the formula (b1-I), R 12 represents a divalent hydrocarbon group which may have a substituent. vinegar. The divalent hydrocarbon group is a divalent aliphatic group, a divalent aromatic ring group, or one or more divalent aliphatic groups. Examples of such groups include a group formed by linking an aromatic group to one or more divalent aromatic ring groups.

[0113] The divalent aliphatic group may be linear, branched, or cyclic. From the viewpoint of solubility, linear chains are preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed area, The number of carbon atoms is usually 1 or more, and preferably 20 or less. It is preferable that the ratio is 15 or less, and more preferably 10 or less. It is easy to obtain a strong film, the surface is less likely to become rough, and adhesion to the substrate tends to be good. By setting the content to the upper limit or less, deterioration of sensitivity and film loss during development can be easily suppressed, and the resolution can be improved. The image quality tends to improve.

[0114] Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, and an n-propylene group. Examples of the aryl group include an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferred from the viewpoint of the rigidity of the skeleton. The divalent branched aliphatic group is a divalent linear aliphatic group having a methyl group as a side chain. Tyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group Examples of the structure include those having a butyl group, a sec-butyl group, a tert-butyl group, etc. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, and 2 or more The value is preferably 12 or less, and more preferably 10 or less. By doing so, a strong film is formed, and the adhesion to the substrate tends to be good. This tends to suppress deterioration of sensitivity and film loss during development, and improve resolution. Specific examples of the cyclic aliphatic group having a valence include a cyclohexane ring, a cycloheptane ring, a cyclohexane ring, Cane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclo Dodecane ring, dicyclopentadiene, dicyclopentane, etc., with two hydrogen atoms removed from the ring Among these, from the viewpoint of the rigidity of the skeleton, a dicyclopentadiene ring, a dicyclopentadiene ring, Groups in which two hydrogen atoms have been removed from a cyclopentane ring or an adamantane ring are preferred.

[0115] The divalent aliphatic group may have a substituent, which may be a carbon atom such as a methoxy group or an ethoxy group. Examples of the alkyl group include an alkoxy group having 1 to 5 carbon atoms; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. Among these, from the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0116] In addition, the divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, and more preferably 6 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting the content to the lower limit or more, a strong film is easily obtained, the surface is less likely to become rough, and the film is easily attached to the substrate. By adjusting the value to the upper limit or less, the deterioration of sensitivity and the This tends to suppress film loss during printing and improve resolution.

[0117] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic or condensed ring. The aromatic hydrocarbon ring group may be, for example, a valence group having two free atoms. Nitrogen ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluorene ring, Examples of such groups include an oranthene ring and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzo ring, and a benzoyl ring having two free valences. Zofran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazo an aryl ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, Pyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothi Azole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidinium ring Aromatic ring, triazine ring, quinoline ring, isoquinoline ring, cinnaline ring, quinoxaline ring, phenanthroline ring, Anthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring , azulene ring and the like. Among these, from the viewpoint of patterning properties, benzene rings or is preferably a naphthalene ring, more preferably a benzene ring having two free valences.

[0118] The substituent that the divalent aromatic ring group may have is a hydroxy group, a methyl group, a methionine group, Examples of the alkyl group include an oxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. However, from the viewpoint of development solubility, it is preferable that the group is unsubstituted.

[0119] In addition, examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include: Examples of the divalent aliphatic group include a group in which one or more of the divalent aromatic ring groups are linked to one or more of the divalent aliphatic groups. Can be obtained. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more. It is usually 10 or less, preferably 5 or less, and more preferably 3 or less. This tends to make it easier to obtain a strong film, less prone to surface roughness, and better adhesion to the substrate. By setting the content to the upper limit or less, deterioration of sensitivity and film loss during development can be easily suppressed. , there is a tendency for the resolution to improve. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, and preferably 2 or more. It is usually 10 or less, preferably 5 or less, and more preferably 3 or less. This tends to make it easier to obtain a strong film, less prone to surface roughness, and better adhesion to the substrate. By setting the content to the upper limit or less, deterioration of sensitivity and film loss during development can be easily suppressed. There is a tendency for the resolution to improve.

[0120] Specific examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include Among these, groups represented by the following formulas (b1-IA) to (b1-IF) can be mentioned. However, from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane, a group represented by the following formula (b1-IA) is preferred. It is nice.

[0121] [ka]

[0122] k represents 1 or 2. From the viewpoint of adhesion and patterning properties, k is preferably 1. From the viewpoint of the NMP resistance described above, k is preferably 2. The relate may contain both a partial structure where k is 1 and a partial structure where k is 2.

[0123] As described above, the benzene ring in formula (b1-I) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, and the like. The number of the substituents is not particularly limited. However, it may be one or two or more. Among these, from the viewpoint of patterning properties, non-substituted groups are preferred.

[0124] From the viewpoint of ease of synthesis, the partial structure represented by the formula (b1-I) may be represented by the following formula: It is preferable that the partial structure is represented by b1-I-1).

[0125] [ka]

[0126] In formula (b1-I-1), R 11 R 12 and k are as defined in formula (b1-I) above. R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond. The benzene ring may be further substituted with any substituent.

[0127] The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrofuran, phthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetraacetate phthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, One selected from the group consisting of lorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid One or more species may be mentioned. Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, and isopropyl alcohol are preferable. Taconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and more preferably tetrahydrofuran. These are tetracarboxylic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

[0128] (b1-I) The compound represented by the formula (b1) contained in one molecule of the epoxy (meth)acrylate resin The partial structure represented by -I-1) may be one or more kinds, for example, R X is a hydrogen atom and R X However, polybasic acid residues may be mixed.

[0129] Also, (b1-I) the epoxy (meth)acrylate resin having the formula The number of partial structures represented by (b1-I) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. More preferably, the ratio is 20 or less, and even more preferably 15 or less. By doing so, it is easier to obtain a strong film and the surface tends to be less prone to roughness. By setting the content to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution is improved. There is a tendency for

[0130] (b1-I) Gel permeation chromatography of epoxy (meth)acrylate resins The weight average molecular weight (Mw) of polystyrene equivalent measured by gel permeation chromatography (GPC) is not particularly limited. However, 1000 or more is preferable, 1500 or more is more preferable, and 2000 or more is even more preferable. More preferably, 3000 or more is more preferable, 4000 or more is particularly preferable, and 50 00 or more is most preferable, and 30,000 or less is preferable, and 20,000 or less is more preferable. It is preferably not more than 10,000, and particularly preferably not more than 8,000. By setting the above to the upper limit or less, the remaining film ratio of the photosensitive coloring composition tends to be good. This tends to improve the resolution.

[0131] The acid value of the epoxy (meth)acrylate resin (b1-I) is not particularly limited, but is preferably 1 0 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mgKOH / g or more is more preferable. OH / g or more is more preferable, 50 mgKOH / g or more is even more preferable, and 80 mgKOH / g or more is even more preferable. gKOH / g or more is particularly preferred, and 200 mgKOH / g or less is preferred, and 150 mgKOH / g or less is particularly preferred. mgKOH / g or less is more preferable, and 130 mgKOH / g or less is even more preferable. It is particularly preferable that the content is 100 mgKOH / g or less. By setting the content to the upper limit or less, the photosensitive coloring composition tends to be improved. The composition tends to have a good film remaining rate.

[0132] Specific examples of the epoxy (meth)acrylate resin (b1-I) are given below. The * in the formula indicates a bond.

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] <(b1-II) Epoxy (meth)acrylate resin> Next, an epoxy (meth)acrylate having a partial structure represented by the general formula (b1-II) is The rate-based resin will now be described in detail.

[0138] [ka]

[0139] In formula (b1-II), R 13 each independently represents a hydrogen atom or a methyl group; R 14 is a circular represents a divalent hydrocarbon group having a hydrocarbon group as a side chain, and R 15 and R 16 are each independently represents a divalent aliphatic group which may have a substituent, and m and n each independently represent an integer of 0 to 2. and * represents a bond.

[0140] (R 14 ) In the general formula (b1-II), R 14 is a divalent cyclic hydrocarbon group having a side chain represents a hydrocarbon group. The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

[0141] The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, and preferably 2 or more. The lower limit is usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting the thickness to the above value, a strong film is easily obtained and the surface tends to be less prone to roughening. By setting the content to the upper limit or less, deterioration of sensitivity and film loss during development can be easily suppressed, and resolution can be improved. There is a tendency to rise. The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, and more preferably 8 or more. It is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. By setting the value to the lower limit or more, a strong film is easily obtained, and the surface By setting the value to the upper limit or less, the deterioration of sensitivity and the development This tends to suppress film loss during printing and improve resolution. Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, Cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring Among these, the photosensitive coloring composition is preferably used in view of the film remaining rate and resolution. From this viewpoint, an adamantane ring is preferred.

[0142] On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, and 2 or more. is preferable, 3 or more is more preferable, and usually 10 or less, 5 or less is preferable, 4 By setting the thickness to the lower limit or more, a strong film is easily obtained and the surface roughness is prevented. By setting the value to the upper limit or less, the deterioration of sensitivity and the film thickness during development tend to be prevented. It is easier to suppress wear and tear, and there is a tendency for resolution to improve. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, and more preferably 10 or more carbon atoms. More preferably, 12 or more is particularly preferred, and 40 or less is preferred, with 30 or less being preferred. More preferably, the ratio is 20 or less, and particularly preferably 15 or less. By doing so, it is easier to obtain a strong film and the surface tends to be less prone to roughness. By setting the content to be equal to or less than the upper limit, patterning characteristics tend to be improved. Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracyclyl ring, and an aryl ring. cene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, Examples of the ring include a ricene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of patterning properties.

[0143] In addition, the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain The group is not particularly limited, but may be, for example, a divalent aliphatic group, a divalent aromatic ring group, one or more divalent Examples of the group include a group in which an aliphatic group is linked to one or more divalent aromatic ring groups.

[0144] The divalent aliphatic group may be linear, branched, or cyclic. From the viewpoint of solubility, linear chains are preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed area, The number of carbon atoms is usually 1 or more, preferably 3 or more, and more preferably 6 or more. More preferably, the number is 25 or less, more preferably 20 or less, and most preferably 15 or less. By setting the content to be equal to or more than the lower limit, a strong film is easily obtained and surface roughness is prevented. In particular, adhesion to the substrate tends to be good, and by setting the value to the upper limit or less, the sensitivity This tends to suppress deterioration of the resistivity and film loss during development, and therefore tends to improve resolution.

[0145] Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, and an n-propylene group. Examples of the aryl group include an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferred from the viewpoint of the rigidity of the skeleton. The divalent branched aliphatic group is a divalent linear aliphatic group having a methyl group as a side chain. Tyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group Examples of the structure include those having a butyl group, a sec-butyl group, a tert-butyl group, etc. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, and 2 or more Preferably, it is equal to or higher than 10, more preferably equal to or lower than 5, and even more preferably equal to or lower than 3. By setting the content to the lower limit or more, a strong film is formed, and the adhesion to the substrate tends to be good. In addition, by setting the temperature to the upper limit or less, deterioration of sensitivity and film loss during development can be easily suppressed, and resolution can be improved. There is a tendency to improve. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclohexane ring, Dodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, Examples of such groups include those in which two hydrogen atoms have been removed from a ring such as a cyclododecane ring. From the viewpoint of rigidity, a group in which two hydrogen atoms have been removed from an adamantane ring is preferred.

[0146] The divalent aliphatic group may have a substituent, which may be a carbon atom such as a methoxy group or an ethoxy group. Examples of the alkyl group include an alkoxy group having 1 to 5 carbon atoms; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. Among these, from the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0147] In addition, the divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, and more preferably 6 or more. It is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting the content to the lower limit or more, a strong film is easily obtained, the surface is less likely to become rough, and the film is easily attached to the substrate. By adjusting the value to the upper limit or less, the deterioration of sensitivity and the This tends to suppress film loss during printing and improve resolution.

[0148] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic or condensed ring. The aromatic hydrocarbon ring group may be, for example, a valence group having two free atoms. Nitrogen ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluorene ring, Examples of such groups include an oranthene ring and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzo ring, and a benzoyl ring having two free valences. Zofran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazo an aryl ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, Pyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothi Azole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidinium ring Aromatic ring, triazine ring, quinoline ring, isoquinoline ring, cinnaline ring, quinoxaline ring, phenanthroline ring, Anthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring Among these, from the viewpoint of patterning properties, two-ring groups are preferred. A benzene ring or a naphthalene ring having two free valences is preferred, and a A benzene ring is more preferred.

[0149] The substituent that the divalent aromatic ring group may have is a hydroxy group, a methyl group, a methionine group, Examples of the alkyl group include an oxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. However, from the viewpoint of development solubility, it is preferable that the group is unsubstituted.

[0150] In addition, examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include: Examples of the divalent aliphatic group include a group in which one or more of the divalent aromatic ring groups are linked to one or more of the divalent aliphatic groups. Can be obtained. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more. It is usually 10 or less, preferably 5 or less, and more preferably 3 or less. This tends to make it easier to obtain a strong film, less prone to surface roughness, and better adhesion to the substrate. By setting the content to the upper limit or less, deterioration of sensitivity and film loss during development can be easily suppressed. , there is a tendency for the resolution to improve. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, and preferably 2 or more. It is usually 10 or less, preferably 5 or less, and more preferably 3 or less. This tends to make it easier to obtain a strong film, less prone to surface roughness, and better adhesion to the substrate. By setting the content to the upper limit or less, deterioration of sensitivity and film loss during development can be easily suppressed. There is a tendency for the resolution to improve.

[0151] Specific examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include Among these, the groups represented by the formulas (b1-IA) to (b1-IF) can be mentioned. However, from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane, the group represented by the above formula (b1-IC) is preferred. It is nice.

[0152] The bonding mode of the cyclic hydrocarbon group, which is a side chain, to these divalent hydrocarbon groups is not particularly limited. However, for example, one hydrogen atom of an aliphatic group or an aromatic ring group may be substituted with the side chain. One example is a mode in which a cyclic hydrocarbon group is formed as a side chain by including one of the carbon atoms of the aliphatic group. do.

[0153] (R 15 , R 16 ) In the general formula (b1-II), R 15 and R 16 Each independently has a substituent. represents a divalent aliphatic group.

[0154] The divalent aliphatic group may be linear, branched, or cyclic. From the viewpoint of solubility, linear chains are preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed area, The number of carbon atoms is usually 1 or more, preferably 3 or more, and more preferably 6 or more. More preferably, the number is 20 or less, more preferably 15 or less, and most preferably 10 or less. By setting the content to be equal to or more than the lower limit, a strong film is easily obtained and surface roughness is prevented. In particular, adhesion to the substrate tends to be good, and by setting the value to the upper limit or less, the sensitivity This tends to suppress deterioration of the resistivity and film loss during development, and therefore tends to improve resolution.

[0155] Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, and an n-propylene group. Examples of the aryl group include an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferred from the viewpoint of the rigidity of the skeleton. The divalent branched aliphatic group is a divalent linear aliphatic group having a methyl group as a side chain. Tyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group Examples of the structure include those having a butyl group, a sec-butyl group, a tert-butyl group, etc. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, and 2 or more The value is preferably 12 or less, and more preferably 10 or less. By doing so, a strong film is formed, and the adhesion to the substrate tends to be good. This tends to suppress deterioration of sensitivity and film loss during development, and improve resolution. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclohexane ring, Dodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, Examples include groups in which two hydrogen atoms have been removed from a ring such as cyclododecane or dicyclopentadiene. Among these, from the viewpoint of the rigidity of the skeleton, the dicyclopentadiene ring and the adamantane ring are preferred. A group having two hydrogen atoms removed therefrom is preferred.

[0156] The divalent aliphatic group may have a substituent, which may be a carbon atom such as a methoxy group or an ethoxy group. Examples of the alkyl group include an alkoxy group having 1 to 5 carbon atoms; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. Among these, from the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0157] (m, n) In the general formula (b1-II), m and n each independently represent an integer of 0 to 2. By setting the content at or above the lower limit, the patterning suitability becomes good and the surface roughness tends to be less likely to occur. In addition, by making the content equal to or less than the upper limit, the developability tends to be good. From this viewpoint, 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 more.

[0158] In addition, the partial structure represented by the general formula (b1-II) has the following properties in terms of adhesion to a substrate: A partial structure represented by the following general formula (b1-II-1) is preferable.

[0159] [ka]

[0160] In formula (b1-II-1), R 13 , R 15 , R 16 m and n are the same as those in formula (b1-II). and R α represents a monovalent cyclic hydrocarbon group which may have a substituent, and p is an integer of 1 or more. The benzene ring in formula (b1-II-1) may further include any substituent. It may be substituted with a substituent.

[0161] (R α ) In the general formula (b1-II-1), R α represents a monovalent ring which may have a substituent. represents a cyclic hydrocarbon group. The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

[0162] The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, and preferably 2 or more. The lower limit is usually 6 or less, preferably 4 or less, and more preferably 3 or less. By doing so, it is easier to obtain a strong film and the surface tends to be less prone to roughness. By setting the content to be equal to or less than the upper limit, patterning characteristics tend to be improved. The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, and more preferably 8 or more. It is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. By making the value equal to or larger than the lower limit, a strong film is easily obtained, and the surface Roughness is less likely to occur, and by setting the value to the upper limit or less, the patterning characteristics are improved. tends to be favorable. Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, Cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring Among these, adamantanic rings are preferred from the viewpoint of strong film properties. The tan ring is preferred.

[0163] On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, and 2 or more. is preferable, 3 or more is more preferable, and usually 10 or less, preferably 5 or less. By setting the content to the lower limit or more, a strong film is easily obtained and the surface tends to be less prone to roughening. By setting the content to be equal to or less than the upper limit of the aforementioned range, the patterning characteristics tend to be good. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 5 or more carbon atoms, and more preferably 6 or more carbon atoms. The lower limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting the thickness to the above value, a strong film is easily obtained and the surface tends to be less prone to roughening. By setting the content to be equal to or less than the upper limit, the patterning characteristics tend to be good. Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracyclyl ring, and an aryl ring. Among these, the benzene ring, the phenanthrene ring, the fluorene ring, etc. From this viewpoint, a fluorene ring is preferred.

[0164] The substituents which the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, butyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, alkyl groups having 1 to 5 carbon atoms, such as amyl and iso-amyl groups; methoxy and ethoxy groups; Examples of the alkyl group include an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a nitro group, a cyano group, and a carboxyl group. Among these, from the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0165] p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. By setting it to the upper limit or less, the degree of film hardening and the film remaining rate tend to be good. This tends to improve developability.

[0166] Among these, from the viewpoint of strong film hardness, R α is preferably a monovalent aliphatic cyclic group. It is preferably an adamantyl group, and more preferably an adamantyl group.

[0167] As described above, the benzene ring in formula (b1-II-1) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, Examples of the substituents include ethyl, ethoxy, propyl, and propoxy groups. There is no particular limit to the number of substituents. The number is not limited, and may be one or two or more. Among these, from the viewpoint of patterning properties, non-substituted groups are preferred.

[0168] Specific examples of the partial structure represented by formula (b1-II-1) are given below.

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] [ka]

[0174] In addition, the partial structure represented by the general formula (b1-II) is effective in improving the rigidity of the skeleton and the hydrophobicity of the membrane. From this viewpoint, a partial structure represented by the following general formula (b1-II-2) is preferable.

[0175] [ka]

[0176] In formula (b1-II-2), R 13 , R 15 , R 16 m and n are the same as those in formula (b1-II). and R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond. The benzene ring in formula (b1-II-2) is further substituted with any substituent. Good too.

[0177] (R β ) In the formula (b1-II-2), R β is a divalent cyclic carbon atom which may have a substituent. Represents a hydrogen atom. The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

[0178] The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, and preferably 2 or more. The ratio is usually 10 or less, and preferably 5 or less. A film is easily obtained and surface roughness is less likely to occur. This tends to suppress deterioration of sensitivity and film loss during development, and improve resolution. The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, and more preferably 8 or more. It is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. By setting the content to be equal to or greater than the lower limit, there is a tendency for film roughness during development to be suppressed, and By setting the value to the value below, it becomes easier to suppress deterioration of sensitivity and film loss during development, and the resolution tends to improve. be. Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring and a cycloheptane ring. , cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane Among these, from the viewpoints of film loss during development and resolution, From the above, an adamantane ring is preferred.

[0179] On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, and 2 or more. is preferable, 3 or more is more preferable, and usually 10 or less, preferably 5 or less. By setting the content to the lower limit or more, a strong film is easily obtained and the surface tends to be less prone to roughening. By setting the content to the upper limit or less, deterioration of sensitivity and film loss can be easily suppressed, and resolution can be improved. There is a tendency to rise. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, and more preferably 10 or more carbon atoms. More preferably, the number is 40 or less, more preferably 30 or less, and even more preferably 20 or less. It is more preferable that the content is 15 or less, and particularly preferable that the content is 15 or less. By making the content equal to or more than the lower limit, a strong film can be obtained. In addition, by setting the value to the upper limit or less, the sensitivity is improved. This tends to suppress deterioration of the optical density and film loss, and improves resolution. Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracyclyl ring, and an aryl ring. Among these, from the viewpoint of developability, Therefore, a fluorene ring is preferred.

[0180] The substituents which the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, butyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, alkyl groups having 1 to 5 carbon atoms, such as amyl and iso-amyl groups; methoxy and ethoxy groups; Examples of the alkyl group include an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a nitro group, a cyano group, and a carboxyl group. Among these, from the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0181] Among these, from the viewpoints of suppressing film loss and resolution, R β is a divalent aliphatic cyclic group and a divalent adamantane ring group is more preferable. On the other hand, from the viewpoint of patterning characteristics, R β is preferably a divalent aromatic ring group. More preferably, it is a divalent fluorene ring group.

[0182] As described above, the benzene ring in formula (b1-II-2) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, Examples of the substituents include ethyl, ethoxy, propyl, and propoxy groups. There is no particular limit to the number of substituents. The number is not limited, and may be one or two or more. In addition, two benzene rings may be linked via a substituent. In this case, the substituent is Examples of the divalent group include -O-, -S-, -NH-, and -CH2-. Among these, from the viewpoint of patterning properties, non-substituted is preferable. From the viewpoint of making it difficult for wear and tear to occur, substitution with a methyl group is preferred.

[0183] Specific examples of the partial structure represented by the formula (b1-II-2) are given below. * indicates a bond.

[0184] [ka]

[0185] [ka]

[0186] [ka]

[0187] [ka]

[0188] On the other hand, the partial structure represented by the formula (b1-II) has a coating film residual rate and patterning characteristics. From this viewpoint, the partial structure represented by the following formula (b1-II-3) is preferable.

[0189] [ka]

[0190] In formula (b1-II-3), R 13 , R 14 , R 15 , R 16 m and n are each represented by the formula (b1-II). is synonymous with R Z represents a hydrogen atom or a polybasic acid residue.

[0191] The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. Furthermore, if another OH group is removed, another molecule represented by formula (b1-II-3) is obtained. R in Z may be shared with R Z Through multiple formula (b1-II-3) may be linked together. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrofuran, acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetra Carboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloro One selected from the group consisting of tetrahydrophthalic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid Or two or more types may be mentioned. Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, and isopropyl alcohol are preferable. Taconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and more preferably tetrahydrofuran. These are tetracarboxylic acid and biphenyltetracarboxylic acid.

[0192] (b1-II) The compound represented by the formula (b The partial structure represented by 1-II-3) may be one or more kinds, for example, R Z is hydrogen Atomic and R Z However, polybasic acid residues may be mixed.

[0193] Also, (b1-II) the above-mentioned compound contained in one molecule of the epoxy (meth)acrylate resin The number of partial structures represented by formula (b1-II) is not particularly limited, but is preferably 1 or more, and more preferably 3. More preferably, it is 20 or less, more preferably 15 or less, and 10 or less is preferable. By setting the thickness to the lower limit or more, a strong film is easily obtained, and surface roughness is not easily caused. By setting the value to the upper limit or less, deterioration of sensitivity and film loss are suppressed. This tends to improve the resolution.

[0194] (b1-II) Gel permeation chromium of epoxy (meth)acrylate resin The weight average molecular weight (Mw) of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited. Although not limited, 1000 or more is preferable, 2000 or more is more preferable, and 3000 or more is more preferable. Preferably 0 or less, more preferably 20,000 or less, and even more preferably 10,000 or less; It is more preferably 7000 or less, and particularly preferably 5000 or less. By setting the content to the upper limit or less, the patterning characteristics tend to be improved. A strong film is easily obtained and the surface tends not to become rough.

[0195] The acid value of the epoxy (meth)acrylate resin (b1-II) is not particularly limited, but is preferably 1 0 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mgKOH / g or more is more preferable. OH / g or more is more preferable, 60 mgKOH / g or more is even more preferable, and 80 mgKOH / g or more is even more preferable. gKOH / g or more is particularly preferred, 100 mgKOH / g or more is most preferred, and 2 00mgKOH / g or less is preferable, 150mgKOH / g or less is more preferable, 120mgKOH / g or less is more preferable. It is more preferable that the content is gKOH / g or less. By setting the content to the lower limit or more, a strong film is easily obtained. By adjusting the content to the upper limit or less, the developing solubility is improved and the resolution is improved. There is a tendency for it to be favorable.

[0196] The carboxyl group-containing epoxy (meth)acrylate resins can be used alone or in combination with Two or more resins may be used in combination. In addition, a part of the above-mentioned carboxyl group-containing epoxy (meth)acrylate resin was mixed with other That is, a carboxyl group-containing epoxy (meth)acrylate may be used in place of the binder resin. The acrylate resin may be used in combination with other binder resins. The ratio of carboxyl group-containing epoxy (meth)acrylate resin in potassium soluble resin 50% by mass or more is preferable, and 60% by mass or more is more preferable. It is more preferable that the content is 0% by mass or more, and particularly preferable that the content is 80% by mass or more. It is usually 100% by mass or less.

[0197] In addition, (b) as an alkali-soluble resin, from the viewpoint of compatibility with pigments, dispersants, etc., 2) It is preferable to use an acrylic copolymer resin. The above-mentioned materials can be preferably used.

[0198] The acrylic copolymer resin is, for example, an ethylenic copolymer having one or more carboxy groups. A saturated monomer (hereinafter referred to as "unsaturated monomer (b2-1)") and another copolymerizable ethylene Examples of the copolymer include a copolymer with a cyclic unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2-2)"). It is possible. Examples of the unsaturated monomer (b2-1) include (meth)acrylic acid, crotonic acid, α- Unsaturated monocarboxylic acids such as chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, Unsaturated dicarboxylic acids such as fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid, or anhydrides;mono (2-(meth)acryloyloxyethyl) succinate;mono (2- Mono[(meth)acryloyloxyethyl] and other divalent or higher polyvalent carboxylic acids ω-Carboxypolycaprolactone mono(meth)acryloxyalkylester; Mono(meth)acrylates and other polymers having a carboxyl group and a hydroxyl group at both ends p-vinylbenzoic acid, and the like. These unsaturated monomers (b2-1) may be used alone or in combination of two or more. can.

[0199] Examples of the unsaturated monomer (b2-2) include N-phenylmaleimide, N-cyclohexylphenylmaleimide, and N-cyclohexylphenylmaleimide. N-substituted maleimides such as cyclohexylmaleimide; Styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methyl aromatic vinyl such as p-vinylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene compound;

[0200] Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (Meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate 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 (polymerization degree 2-10) mono (Meth)acrylate, polypropylene glycol (polymerization degree 2-10) mono(meth)acrylate acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, Tricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate, dicyclopentadiene butyl acrylate, glycerol mono(meth)acrylate, 4-hydroxyethyl acrylate Diphenyl (meth)acrylate, ethylene oxide modified paracumylphenol (meth) (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl Methyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, (Meth)acryloyloxymethyl)-3-ethyloxetane and other (meth)acryloyloxymethyl esters of aryl acids;

[0201] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2. 1.0 2,6 ]Decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether vinyl ethers such as 3-(vinyloxymethyl)-3-ethyloxetane; Polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate Mono(meth)acryloyl groups are attached to the ends of polymer chains such as acrylates and polysiloxanes. Examples include chromonomers. These unsaturated monomers (b2-2) may be used alone or in combination of two or more. can.

[0202] In a copolymer of an unsaturated monomer (b2-1) and an unsaturated monomer (b2-2), the copolymer The copolymerization ratio of the unsaturated monomer (b2-1) in the copolymer is preferably 5 to 50 mass %, more preferably The unsaturated monomer (b2-1) is copolymerized in such a range. By this, it is possible to obtain a photosensitive coloring composition having excellent alkali developability and storage stability. There is a tendency to be able to.

[0203] Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include: For example, JP-A-7-140654, JP-A-8-259876, JP-A-10- 31308 Publication, Japanese Patent Application Publication No. 10-300922, Japanese Patent Application Publication No. 11-174224 , JP 11-258415 A, JP 2000-56118 A, JP 2004- Examples of the copolymer include those disclosed in Japanese Patent Application Publication No. 101728. The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method. For example, the method described in JP-A-2003-222717 and JP-A-2006 The methods disclosed in WO 2007 / 029871 and the like This makes it possible to control the structure, Mw, and Mw / Mn.

[0204] In addition, WO 2016 / 194619 and WO 2017 / 1544 The resins described in Publication No. 39 may also be used.

[0205] <(c) Photopolymerization initiator> (c) The photopolymerization initiator directly absorbs light, undergoes a decomposition reaction or a hydrogen abstraction reaction, and polymerizes. A component that has the function of generating reactive radicals. If necessary, a polymerization accelerator (chain transfer agent) Additives such as dyes and sensitizing dyes may be added to the emulsion. Examples of the photopolymerization initiator include those described in JP-A-59-152396 and JP-A-61-152396. Metallocene compounds including titanocene compounds described in JP 2000-56 Hexaarylbiimidazole derivatives described in JP-A-10-39503 Halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in α-Aminoalkylphenone derivatives; JP 2000-80068 A; and oxime ester compounds described in US Pat. No. 5,375,360. .

[0206] Specifically, for example, the metallocene compound is dicyclopentadienyltitanium. Dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl Titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadiene Titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), di Cyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), Dicyclopentadienyltitanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyl Titanium di(2,4-difluorophenyl) chloropentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl) -yl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl) dicyclopentadienyltitanium [2,6-difluoro-3-(pyridyl) (phenyl-1-yl)-phenyl-1-yl, and the like.

[0207] In addition, the 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, (4'-methoxyphenyl)-4,5-diphenylimidazole Examples include dazole dimer.

[0208] 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-trichloro 5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxy Sadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc. Some examples include:

[0209] 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, 2-(4-ethoxycarbonyl naphthyl)-4,6-bis(trichloromethyl)-s-triazine and the like.

[0210] In addition, α-aminoalkylphenone derivatives include 2-methyl-1[4-(methyl Thio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylamino 4-Dimethylaminoisoamylbenzoate, 4-Diethylamino Cetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-di Methylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexa Non, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(di ethylamino) chalcone, etc.

[0211] As photopolymerization initiators, oxime ester compounds are particularly effective in terms of sensitivity and plate making properties. This is especially true when using an alkali-soluble resin containing a phenolic hydroxyl group. Oxime ester compounds having excellent sensitivity are useful. The structure contains a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals. Because it has a structure that allows it to be highly sensitive even in small amounts, it is stable against thermal reactions, and It is possible to obtain a highly sensitive photosensitive coloring composition with a small amount.

[0212] As the oxime ester compound, for example, a compound represented by the following general formula (IV) is Some examples include:

[0213] [ka]

[0214] In the above formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or represents an aromatic ring group which may have a substituent. R 21b represents an optional substituent containing an aromatic ring. R 22a represents an alkanoyl group which may have a substituent, or The aryl group is represented by the formula: n represents an integer of 0 or 1.

[0215] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but may be determined from the viewpoint of solubility in a solvent and sensitivity. From this viewpoint, the number is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 20 or less. More preferably, it is 10 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, and a proline group. Examples of the aryl group include cyclopentyl and cyclopentylethyl groups. Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, Halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include methylphenyl group and N-acetyl-N-acetoxyamino group, which are easy to synthesize. From the viewpoint of functionality, it is preferably unsubstituted.

[0216] R 21a Examples of the aromatic ring group in the formula (I) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but from the viewpoint of solubility in the photosensitive coloring composition, From the viewpoint of developability, it is preferably 30 or less. , more preferably 20 or less, and even more preferably 12 or less.

[0217] Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferred, A phenyl group is more preferred. The substituents which the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, , amino group, amide group, alkyl group, alkoxy group, and groups in which these substituents are linked together. From the viewpoint of developability, alkyl groups, alkoxy groups, and groups formed by linking these groups are preferred. , linked alkoxy groups are more preferred. Among these, from the viewpoint of developability, R 21a is an aromatic ring group which may have a substituent. It is preferable that the aromatic ring group has an alkoxy group as a substituent linked thereto. More preferred.

[0218] Also, R 21b As the aryl group, a carbazolyl group which may be substituted, Examples of the aryl group include an optionally substituted thioxanthonyl group and an optionally substituted diphenyl sulfide group. Among these, an optionally substituted carbazolyl group is preferred from the viewpoint of sensitivity. On the other hand, from the viewpoint of electrical reliability, it is preferable that the diphenyl sulfide group, which may be substituted, is preferable.

[0219] Also, R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but the solubility in the solvent is also important. From the viewpoint of sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 1 It is 5 or less, more preferably 10 or less, and further preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group. Can be obtained. The substituents which the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, and the like. From the viewpoint of ease of synthesis, an unsubstituted group is preferable. It is preferable that the aryl group is an alkyl group.

[0220] Also, R 22a The number of carbon atoms in the aryloyl group is not particularly limited, but the solubility in the solvent is also important. From the viewpoint of sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 1 5 or less, more preferably 10 or less. Specific examples of the aryloyl group include benzoyl. group, naphthoyl group, and the like. The substituents which the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, and the like. From the viewpoint of ease of synthesis, free radicals are preferred. It is preferable that the aryl group is an alkyl group. Among these, from the viewpoint of sensitivity, R 22a is an optionally substituted alkanoyl group is preferably an unsubstituted alkanoyl group, more preferably an acetyl group. It is even more preferable that:

[0221] In addition, the initiator described in JP 2016-133574 A also prevents the color of the liquid crystal layer from being changed by the colorant. It is also suitable for use in that it reduces contamination.

[0222] The photopolymerization initiator may be used alone or in combination of two or more. . The photopolymerization initiator may be, if necessary, a compound that responds to the wavelength of the image exposure light source in order to increase the sensitivity. The sensitizing dye and polymerization accelerator can be blended. xanthene dyes described in JP-A-21958 and JP-A-4-219756; Coumarin colorants having heterocycles as described in JP-A-239703 and JP-A-5-289335 The 3-keto group described in JP-A-3-239703 and JP-A-5-289335 is Marine compounds, pyrromethene dyes described in JP-A-6-19240, and others, Publication No. 7-2528, Japanese Patent Application Publication No. 155292-1982, Publication No. 37377-1977 , JP-A-48-84183, JP-A-52-112681, JP-A-58-15 No. 503, JP-A-60-88005, JP-A-59-56403, JP-A-Hei No. 2-69, JP-A-57-168088, JP-A-5-107761, Dialkylamino compounds described in JP-A-5-210240 and JP-A-4-288818 Examples of the dye include dyes having a benzene skeleton.

[0223] Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are The compounds having an amino group and a phenyl group in the same molecule are particularly preferred. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, Zofenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone Nonobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazo 2-(p-Diethylaminophenyl)benzoxazole, 2-(p-Dimethylaminophenyl)benzoxazole p-Dimethylaminophenyl)benzo[4,5]benzoxazole ) Benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl) -1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-Diethylaminophenyl)benzothiazole, 2-(p-Dimethylaminophenyl)benzothiazole 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-di (p-methylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-di (p-methylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-di p-methylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. Among these, the most preferred are 4, It is a 4'-dialkylaminobenzophenone. The sensitizing dyes may be used alone or in combination of two or more kinds.

[0224] Examples of the polymerization accelerator include ethyl p-dimethylaminobenzoate and 2-dimethylbenzoate. Aromatic amines such as ethylaminoethyl, n-butylamine, and N-methyldiethanolamine The polymerization accelerator may be a single type of aliphatic amine, or a mercapto compound, which will be described later. They may be used alone or in combination of two or more.

[0225] <(d) Ethylenically unsaturated compounds> The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. By including the hydrophilic unsaturated compound, the sensitivity is improved. The ethylenically unsaturated compound used in the present invention has a small number of ethylenically unsaturated groups in the molecule. Specifically, for example, (meth)acrylic acid, (meth)acrylic Alkyl ester of carboxylic acid, acrylonitrile, styrene, and one ethylenically unsaturated bond and monoesters of polyhydric or monohydric alcohols.

[0226] In the present invention, in particular, a polyfunctional ethylenically unsaturated group having two or more ethylenically unsaturated groups in one molecule is used. It is preferable to use a polyfunctional ethylenic monomer. The number of saturated groups is not particularly limited, but is usually 2 or more, preferably 4 or more. More preferably, it is 5 or more, and more preferably, it is 8 or less, and more preferably, it is 7 or more. By setting the value to the lower limit or more, the sensitivity tends to be high, and by setting the value to the upper limit or less, This tends to improve the solubility in the solvent. Examples of polyfunctional ethylenic monomers include aliphatic polyhydroxy compounds and unsaturated carboxy compounds. esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; Polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds esters obtained by esterification with unsaturated carboxylic acids and polybasic carboxylic acids etc.

[0227] The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid may be ethylene Glycol diacrylate, triethylene glycol diacrylate, trimethylol propionate Trimethylolethane triacrylate, Pentaerythritol triacrylate Pentaerythritol diacrylate, Pentaerythritol triacrylate, Pentaerythritol tetraacrylate Dipentaerythritol tetraacrylate, Dipentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, Dipentaerythritol Hexaacrylate, Glycerol Acrylate Acrylates and other aliphatic polyhydroxy compounds, such as acrylates, and acrylates of these exemplary compounds. Methacrylate esters are substituted for acrylates, and itaconates are substituted for methacrylates. Itaconic acid ester, crotonate ester instead of chlorate, or maleate ester instead Maleic acid esters and the like are also included.

[0228] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone. diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, Aromatic polyhydroxy compounds such as ruthenium dimethacrylate and pyrogallol triacrylate Examples of the acrylic acid esters and methacrylic acid esters of the above-mentioned compounds include acrylic acid esters and methacrylic acid esters of the above-mentioned compounds.

[0229] Esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyhydric hydroxy compounds The ester obtained by the above method is not necessarily a single substance, but typical examples include , acrylic acid, phthalic acid, and ethylene glycol condensation product, acrylic acid, maleic acid, and diethylene glycol condensation products, methacrylic acid, terephthalic acid and pentaerythritol Examples of such condensates include condensates of butanediol, acrylic acid, adipic acid, butanediol and glycerin. Can be obtained.

[0230] Other examples of the polyfunctional ethylenic monomers that can be used in the present invention include polyisocyanates. Compounds and hydroxyl group-containing (meth)acrylic esters or polyisocyanate compounds and poly Urethane obtained by reacting ol and hydroxyl group-containing (meth)acrylic acid ester (Meth)acrylates; Polyepoxy compounds and hydroxy (meth)acrylates or ( Epoxy acrylates such as the addition products with methacrylic acid; ethylene bis(meth)acrylic acid; acrylamides such as diphenyl amide; allyl esters such as diallyl phthalate; divinyl phthalate Vinyl group-containing compounds such as acrylates are useful.

[0231] Examples of the urethane (meth)acrylates include DPHA-40H and UX-5. 000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.) ), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-3 2P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, U F-8001G (Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-76 05B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), etc.

[0232] Among these, (d) as an ethylenically unsaturated compound, (meth)aryl is preferred from the viewpoint of curability. It is preferable to use an alkyl acrylate ester, and dipentaerythritol hexaacrylate is preferable. It is more preferable to use a relation. These may be used alone or in combination of two or more.

[0233] <(e) Solvent> The photosensitive coloring composition of the present invention contains a solvent (e). By containing the solvent (e), the pigment can be dissolved. This makes it possible to disperse the agent in the agent and makes it easy to apply. The photosensitive coloring composition of the present invention generally comprises (a) a colorant, (b) an alkali-soluble resin, ) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and if necessary, Various other materials that can be used are dissolved or dispersed in a solvent. From the viewpoint of dispersibility and coatability, organic solvents are preferred.

[0234] Among organic solvents, select those with a boiling point in the range of 100 to 300°C from the viewpoint of coating properties. It is preferable to select a solvent having a boiling point in the range of 120 to 280°C. The boiling point here means the boiling point at a pressure of 1013.25 hPa. The same is true for all.

[0235] Examples of such organic solvents include the following: Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Pyrene glycol monomethyl ether, propylene glycol monoethyl ether, Pyrene 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, di Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether , 3-Methoxybutanol, 3-Methyl-3-Methoxybutanol, Triethylene Glyco glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoalkyl ethers such as glycol methyl ether; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene Glycol dialkyl ethers such as glycol dimethyl ether;

[0236] Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether butyl 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 Glyco Monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate Acetate, Methoxypentyl Acetate, Diethylene Glycol Monomethyl Ether Acetate diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate No-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate acetate, triethylene glycol monomethyl ether acetate, triethylene glycol Monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, etc. Recall alkyl ether acetates; Ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6 - glycol diacetates such as hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, Dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether Ethers such as;

[0237] Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, Diisoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl Ketones, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl Ketones such as ketone, methyl nonyl ketone, methoxymethyl pentanone; Ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene Pyrene glycol, triethylene glycol, methoxymethyl pentanol, glycerin , monohydric or polyhydric alcohols such as benzyl alcohol; n-Pentane, n-Octane, Diisobutylene, n-Hexane, Hexene, Isoprene aliphatic hydrocarbons such as dipentene and dodecane; Cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl Alicyclic hydrocarbons such as;

[0238] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, acetic acid Amyl, methyl isobutyrate, ethylene glycol acetate, ethyl propionate , Propyl propionate, Butyl butyrate, Isobutyl butyrate, Methyl isobutyrate, Ethyl caprylate acrylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate , ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, Buty 3-methoxypropionate linear or cyclic esters such as γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid kind; Halogenated hydrocarbons such as butyl chloride, amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile.

[0239] Commercially available organic solvents that fall into the above category include mineral spirits, Valsol #2, and Apco. #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Sorbet #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyric Acid Cellosolve is a registered trademark of the company. Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme ( (All are product names) These organic solvents may be used alone or in combination of two or more kinds.

[0240] When forming colored spacers by photolithography, the boiling point of the organic solvent is It is preferable to select a temperature range of 100 to 200°C. More preferably, it is 120 to 170°C. It has a boiling point of ℃.

[0241] Among the above organic solvents, the one having a good balance of coating properties, surface tension, etc., and Glycol alkyl ether acetates are preferred because of their relatively high solubility. The glycol alkyl ether acetates may be used alone, but should not be used in combination with other active ingredients. An organic solvent may be used in combination. As the organic solvent to be used in combination, glycol monoacetate is particularly preferred. Among them, propylene glycol is particularly preferred due to its solubility in the components of the composition. Cholesterol monomethyl ether is preferred. Glycol monoalkyl ethers are polar If the amount added is too large, the pigment tends to aggregate, and the viscosity of the photosensitive coloring composition obtained later increases. As a result, the storage stability tends to decrease, such as the temperature rising. The proportion of alkyl ethers is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass. This is more preferable.

[0242] In addition, organic solvents with a boiling point of 150°C or higher (hereinafter sometimes referred to as "high boiling point solvents") It is also preferable to use such a high boiling point solvent in combination. The composition will be slow to dry, but the uniform dispersion of the pigment in the composition will be lost due to rapid drying. For example, the tip of the slit nozzle is This has the effect of preventing the occurrence of defects caused by the precipitation and solidification of colorants, etc. Among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether is particularly preferred because of its high ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol Cholemonoethyl ether acetate is preferred.

[0243] When a high-boiling point solvent is used in combination, the content of the high-boiling point solvent in the organic solvent should be 3% by mass to 50% by mass. % by mass is preferable, 5% by mass to 40% by mass is more preferable, and 5% by mass to 30% by mass is particularly preferable. By setting the value to be equal to or greater than the lower limit, for example, the coloring material may be prevented from precipitating or solidifying at the tip of the slit nozzle. In addition, by keeping the content below the upper limit, it is possible to suppress the occurrence of defects caused by the oxidation of the particles. This prevents the drying temperature of the composition from slowing down, and prevents poor tact time in the reduced pressure drying process and prebaking. This tends to reduce problems such as pin marks on the surface of the material.

[0244] In addition, the high boiling point solvent with a boiling point of 150°C or more is glycol alkyl ether acetate. Alternatively, it may be a glycol alkyl ether. In this case, it has a boiling point of 1 It is not necessary to separately add a high boiling point solvent of 50°C or higher. As a preferred high boiling point solvent, for example, diethylene glycol monohydrate is preferred among the above-mentioned various solvents. -n-Butyl Ether Acetate, Diethylene Glycol Monoethyl Ether Acetate , Dipropylene glycol methyl ether acetate, 1,3-butylene glycol di acetate, 1,6-hexanol diacetate, triacetin, etc.

[0245] <(f) Dispersant> The photosensitive coloring composition of the present invention contains (f) a dispersant. (a) The colorant can be stably dispersed. The dispersant (f) in the photosensitive coloring composition of the present invention is a cyclic compound represented by the following general formula (1): A dispersant (f1) having a repeat unit (hereinafter sometimes referred to as "dispersant (f1)") Contains.

[0246] [ka]

[0247] (In formula (1), R 1 and R 2 each independently represents an alkyl group which may have a substituent, or R is an optionally substituted aryl group. 1 and R 2 are bonded together to form a ring structure You may do so. R 3 is an alkylene group. R 4 is a polycyclic aromatic hydrocarbon group which may have a substituent. R 5 is a hydrogen atom or a methyl group. X is a divalent linking group. Y is a halogen atom.

[0248] The dispersant (f1) is a compound having an ammonium group and a halogen ion having a polycyclic aromatic hydrocarbon group. Dispersants with ammonium groups are irradiated with ultraviolet light. When this happens, some of the bonds that make up the ammonium group may break and become free, but the dispersant (f The polycyclic aromatic hydrocarbon group in 1) has UV absorption properties, so the bond is not broken even when exposed to UV light. It is believed that it is less likely to break or become detached, and is less likely to affect the voltage retention rate after exposure to UV rays. .

[0249] On the other hand, when forming the alignment film, as described later, a solvent (N-methylpyrrolidone, NMP ) may be used, but the dispersant (f1) has chemical resistance to the solvent (NMP resistance) This is because polycyclic aromatic hydrocarbon groups, which are highly hydrophobic and have low polarity, tend to be favorable. The presence of functional groups reduces the solubility of the dispersant in NMP, improving chemical resistance. It is estimated that

[0250] (R 1 and R 2 ) In the formula (1), R 1 and R 2 each independently represents an alkyl group which may have a substituent A group, or an aryl group which may have a substituent. R 1 and R 2 The alkyl group in the formula (I) may be a straight-chain, branched-chain, or cyclic alkyl group. From the viewpoints of voltage retention rate after ultraviolet irradiation and NMP resistance, a straight-chain structure is preferred. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 10 or less, and more preferably 6 or less. It is more preferable that the ratio is 2 or less, and is usually 1 or more. There is a tendency for stability over time to improve. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. From the viewpoint of stability over time of the dispersion, methyl and ethyl groups are preferred. A methyl group is preferred, and a methyl group is more preferred. The substituent that the alkyl group may have is an alkoxy group such as a methoxy group or an ethoxy group. oxy group; halogen atoms such as fluorine, chlorine, and bromine; benzyl group, phenethyl Aralkyl groups such as aryl groups, phenyl groups, naphthyl groups, etc., From the viewpoint of chemical properties, it is preferably unsubstituted.

[0251] R 1 and R 2 The aryl group in the formula (I) is a monovalent aromatic hydrocarbon ring group or a monovalent aromatic Examples of the heterocyclic group include heterocyclic groups. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 24 or less, and more preferably 18 or less. It is preferable that the dispersion ratio is 12 or less, more preferably 12 or less, and usually 6 or more. There is a tendency for sexual activity to improve. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. From the viewpoint of dispersibility, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. stomach. The substituents which the aryl group may have include alkyl groups such as methyl and ethyl groups. ; alkoxy groups such as methoxy and ethoxy groups; fluorine atoms, chlorine atoms, bromine atoms, etc. Halogen atoms; aralkyl groups such as benzyl and phenethyl groups, etc., From this viewpoint, it is preferably unsubstituted.

[0252] In the formula (1), R 1 and R 2 may be bonded to each other to form a ring structure, Examples of the structure include a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a structure formed by condensing two of these rings. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. It is preferable. Specifically, the following can be mentioned.

[0253] [ka]

[0254] (These cyclic structures may further have a substituent. * represents a bond.)

[0255] Among these, R 1 and R 2 Each Each of the alkyl groups is preferably an alkyl group which may have a substituent, and each of the alkyl groups is preferably an unsubstituted alkyl group. More preferably, it is a methyl group or an ethyl group, and still more preferably, it is a methyl group or an ethyl group. A ethyl group is particularly preferred.

[0256] (R 3 ) In the formula (1), R 3 is an alkylene group. The alkylene group may be a linear, branched, or cyclic alkyl group. From the viewpoint of ease, a straight chain is preferred. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 10 or less, and more preferably 6 or less. It is preferable that the ratio is 2 or less, more preferably 2 or less, and usually 1 or more. It tends to be easier. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. From the viewpoint of ease of synthesis, preferred are methylene, ethylenediamine ... A ethylene group is preferred, and a methylene group is more preferred.

[0257] (R 4 ) In the formula (1), R 4 is a polycyclic aromatic hydrocarbon group which may have a substituent. do. A polycyclic aromatic hydrocarbon group is a group in which aromatic hydrocarbon rings are condensed, and The number of rings in the group is not particularly limited as long as it is 2 or more, and is preferably 5 or less, and more preferably 4 or less. By making the content equal to or more than the lower limit, NMP resistance and ultraviolet ray irradiation resistance are improved. By setting the content to the upper limit or less, the dispersibility becomes good. There is a tendency for

[0258] The number of aromatic rings in the polycyclic aromatic hydrocarbon group is not particularly limited, and is usually 2 or more. However, it is not particularly limited, and is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. By setting the value to be equal to or more than the lower limit, the NMP resistance and the voltage retention rate after ultraviolet irradiation tend to be good. By setting the content to the upper limit or less, the dispersibility tends to be good.

[0259] In addition, when the polycyclic aromatic hydrocarbon group has a benzene ring, the number of the benzene rings is not particularly limited. Generally, the number is 1 or more, preferably 2 or more, and is preferably 5 or less, more preferably 4 or less. By setting the value to be equal to or more than the lower limit, the NMP resistance and the electric field after irradiation with ultraviolet rays can be improved. The pressure retention rate tends to be good, and by setting the pressure to the upper limit or less, the dispersibility is good. There is a tendency for

[0260] The number of carbon atoms in the polycyclic aromatic hydrocarbon group is not particularly limited, but is preferably 7 or more, and more preferably 8 or more. It is more preferable that the number of the sieving members is 9 or more, and more preferable that the number of the sieving members is 18 or less, and more preferable that the number of the sieving members is 16 or less. It is preferable that the value is equal to or less than the lower limit, more preferably equal to or less than 14, and particularly preferably equal to or less than 12. In addition, the NMP resistance and the voltage retention rate after ultraviolet irradiation tend to be good at or below the upper limit. By adjusting the amount of the mixture to be lower than 100g, the dispersibility tends to be improved.

[0261] Specific examples of the polycyclic aromatic hydrocarbon group include an azulenyl group, a naphthyl group, and an anthracenyl group. group, phenanthrenyl group, fluorenyl group, tetracenyl group, chrysenyl group, benzfluor From the viewpoint of NMP resistance, naphthyl, anthracenyl, is preferred, and a naphthyl group is more preferred.

[0262] The substituents which the polycyclic aromatic hydrocarbon group may have include a methyl group, an ethyl group, etc. Alkyl groups; alkoxy groups such as methoxy and ethoxy groups; fluorine atoms, chlorine atoms, bromine atoms halogen atoms such as benzyl and phenethyl groups; and aralkyl groups such as benzyl and phenethyl groups. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0263] Specific examples of the polycyclic aromatic hydrocarbons constituting the polycyclic aromatic hydrocarbon group are given below.

[0264] [ka]

[0265] (X) In the above formula (1), X is a divalent linking group. Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, and a cyclic alkyl group having 6 to 8 carbon atoms. 12 arylene groups, -CONH-R6 -group, -COOR 7 - group (wherein R 6 and R 7 Each each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms ( From the viewpoint of dispersibility, -COOR 7 -group is preferred. 7 Among them, from the viewpoint of the stability of the dispersion liquid over time, alkylene having 1 to 10 carbon atoms is preferred. An alkylene group having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 3 carbon atoms is more preferred. More preferred is a phenyl group.

[0266] (Y) In the above formula (1), Y is a halogen atom. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. From the viewpoint of ease of synthesis, a chlorine atom or a bromine atom is preferred, and a chlorine atom is more preferred.

[0267] The dispersant (f1) has a repeating unit represented by the general formula (1) above. It may also have other repeating units. Dispersant (f1) is used from the viewpoint of preventing the generation of foreign matter during die coating (re-dissolving ability). It is preferable that the repeating unit has the following general formula (2).

[0268] [ka]

[0269] (In formula (2), R 8 and R 9 each independently represents an alkyl group which may have a substituent, or R is an optionally substituted aryl group. 8 and R 9 are bonded together to form a ring structure You may do so. R 10 is a hydrogen atom or a methyl group. Z is a divalent linking group.

[0270] In the formula (2), R 8 and R 9 each independently represents an alkyl group which may have a substituent A group which may have a substituent, or an aryl group which may have a substituent. The aryl group and the aryl group which may have a substituent are R 1 ~R 3 and The above-mentioned materials can be preferably used.

[0271] In the formula (2), R 8 and R 9 may be bonded to each other to form a ring structure. Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring and a condensed structure formed by condensing two of these rings. The nitrogen-containing heterocycle is preferably one not having aromaticity, and more preferably a saturated ring. Specifically, the following are included:

[0272] [ka]

[0273] (These cyclic structures may further have a substituent. * represents a bond.)

[0274] In the formula (2), Z is a divalent linking group. The divalent linking group is represented by the formula (1 ) can be preferably used as X.

[0275] In addition, the dispersant (f1) enhances compatibility with solvents and alkali-soluble resins and improves dispersion stability. From the viewpoint of improving the above properties, it is preferable that the polymerizable compound has a repeating unit represented by the following general formula (3): I wish.

[0276] [ka]

[0277] (In formula (3), R 11 represents a hydrogen atom, an alkyl group which may have a substituent, or It is an aryl group which may be present. R 12 is a hydrogen atom or a methyl group.

[0278] (R 11 ) R 11 The alkyl group in the formula (I) may be a straight-chain, branched-chain, or cyclic alkyl group. From the viewpoint of compatibility with solvents and alkali-soluble resins, it is preferable that the chain structure is linear. From the viewpoint of affinity for pigments, it is preferably branched. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and more preferably 4. More preferably, the number is 10 or less, more preferably 8 or less, and even more preferably 6 or less. By setting the content to be equal to or greater than the lower limit, there is a tendency for the affinity to the pigment to be increased. By adjusting the content to the upper limit or less, the compatibility with solvents and alkali-soluble resins is improved, and dispersibility is improved. There is a tendency for Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples include hexyl, heptyl, octyl, and ethylhexyl groups. From the viewpoint of compatibility with the alkali-soluble resin, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. The substituent that the alkyl group may have is an alkoxy group such as a methoxy group or an ethoxy group. oxy group; halogen atoms such as fluorine, chlorine, and bromine; phenyl and naphthyl groups From the viewpoint of compatibility with solvents and alkali-soluble resins, It is preferably unsubstituted, and from the viewpoint of affinity for pigments, it is preferably a phenyl group. I wish.

[0279] R 11 The aryl group in the formula (I) is a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic ring group. Examples of such groups include The number of carbon atoms in the aryl group is not particularly limited, but is usually 6 or more and preferably 16 or less. It is preferable that the number of the slits is 12 or less, more preferably 6 or less. It tends to increase affinity for the material. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. From the viewpoint of dispersibility, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. stomach. The substituents which the aryl group may have include alkyl groups such as methyl and ethyl groups. ; alkoxy groups such as methoxy and ethoxy groups; fluorine atoms, chlorine atoms, bromine atoms, etc. Halogen atoms; aryl groups such as phenyl and naphthyl groups; benzyl and phenethyl groups From the viewpoint of dispersibility, it is preferable that the alkyl group is unsubstituted.

[0280] Among these, from the viewpoint of compatibility with solvents and alkali-soluble resins, R 11 As An alkyl group which may have a substituent is preferable, and an unsubstituted alkyl group is more preferable. More preferred are methyl, butyl, or ethylhexyl groups.

[0281] From the viewpoint of compatibility with solvents and alkali-soluble resins, the dispersant (f1) should be one of the following: It is preferable that the repeating unit has the general formula (4):

[0282] [ka]

[0283] (In formula (4), R 13 is a methylene group, an ethylene group, or a propylene group. R 14 is a methyl group, an ethyl group, or a propyl group. R 15 is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

[0284] R 13 The olefins are methylene, ethylene, or propylene groups, but are solvent- or alkali-soluble resins. From the viewpoint of compatibility with fats, an ethylene group is preferred. R 14 The aryl group is a methyl group, an ethyl group, or a propyl group, but it is highly resistant to solvents and alkali-soluble resins. From the viewpoint of compatibility, a methyl group or an ethyl group is preferred, and an ethyl group is more preferred.

[0285] n is an integer of 1 to 20, preferably 1 or more, more preferably 2 or more, and more preferably 10 By setting the value to the lower limit or more, the solvent and alkali can be easily used. In addition, by setting the content of the pigment to the upper limit or less, the compatibility with the soluble resin tends to be improved. It tends to increase the affinity for the substance and improve dispersibility.

[0286] The repeating unit represented by the general formula (1) in the dispersant (f1) (hereinafter, “repeating unit”) The content ratio of the repeating unit (1) is not particularly limited, but In the range, 1 mol % or more is preferable, 4 mol % or more is more preferable, and 6 mol % or more is even more preferable. It is preferably 8 mol % or more, particularly preferably 40 mol % or less, and more preferably 20 mol % or less. It is more preferably 15 mol % or less, further preferably 10 mol % or less. By setting the content to the lower limit or more, the temporal stability of the dispersion liquid tends to be good. By setting the content to be equal to or less than the upper limit, the dispersibility tends to be good.

[0287] The dispersant (f1) is a repeating unit represented by the general formula (2) (hereinafter, “repeating unit”). (2)" is sometimes referred to as ". In the case where the composition contains the above-mentioned amine compound, the content ratio is not particularly limited, but In the total repeating units, 1 mol% or more is preferable, 5 mol% or more is more preferable, and 10 mol% or more is more preferable. More preferably, the content is 15 mol % or more, particularly preferably 15 mol % or more, and more preferably 50 mol % or less. Preferably, the content is 40 mol % or less, more preferably 30 mol % or less, and even more preferably 20 mol % or less. By making the content equal to or more than the lower limit, the dispersibility tends to be good. By adjusting the content to be equal to or less than the upper limit, the temporal stability of the dispersion tends to be good.

[0288] When the dispersant (f1) contains the repeating unit (2), it is preferably a repeating unit (1) and The content of the repeating unit (1) relative to the total of the repeating units (2) is usually 5 mol % or more. 10 mol % or more is preferable, 20 mol % or more is more preferable, and 25 mol % or more is even more preferable. It is preferably 30 mol % or more, particularly preferably 30 mol % or more, and usually 100 mol % or less, and more preferably 80 mol % or less. % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less. By making the content equal to or more than the lower limit, the stability over time of the dispersion liquid is good. By setting the value to the upper limit or less, the voltage holding ratio after ultraviolet irradiation and NMP Tends to be well tolerated.

[0289] The dispersant (f1) is a repeating unit represented by the general formula (3) (hereinafter, “repeating unit”). (3)" is sometimes referred to as ". In the case where the composition contains the above-mentioned amine compound, the content ratio is not particularly limited, but It is preferably 20 mol % or more, more preferably 40 mol % or more, of all repeating units, and more preferably 50 mol % or more. % or more, more preferably 60 mol % or more, particularly preferably 90 mol % or less. The lower limit is preferably 80 mol % or less, more preferably 75 mol % or less. By setting the content to be equal to or more than the upper limit, there is a tendency for the affinity for the pigment to be increased. This tends to increase the compatibility with solvents and alkali-soluble resins.

[0290] The dispersant (f1) is a repeating unit represented by the general formula (4) (hereinafter, “repeating unit”). (4)" is sometimes referred to as ". In the case where the composition contains the above-mentioned amine compound, the content ratio is not particularly limited, but The content of the repeating units is preferably 0.5 mol % or more, more preferably 1 mol % or more, and more preferably 2 mol % or more. % or more, more preferably 2.5 mol % or more, particularly preferably 10 mol % or less. It is preferably 8 mol % or less, more preferably 5 mol % or less, and even more preferably 3 mol % or less. By setting the content to the lower limit or more, compatibility with solvents and alkali-soluble resins is improved. By setting the content to the upper limit or less, the affinity for the pigment tends to be increased. There is.

[0291] When the dispersant (f1) has the repeating unit (1) and the repeating unit (2), the dispersibility From the viewpoint of repeating units (1) and (2), a block B having a repeating unit (1) and a block B having a repeating unit (2) A block copolymer having a unit (1) and an A block having no repeating unit (2). It is preferable that the block copolymer is an AB block copolymer or an ABA block copolymer. It is preferable that the copolymer is a styrene copolymer.

[0292] In the B block, the repeating unit (1) and the repeating unit (2) are randomly copolymerized. In the case of the repeating unit (1), the repeating unit may be contained in any form of block copolymer. and repeating unit (2) may each be contained in block B in two or more kinds. In this case, each repeating unit is randomly or block-copolymerized in the B block. They may be contained in any of the above forms.

[0293] When the dispersant (f1) has a repeating unit (3) or a repeating unit (4), they are A It may be contained in a block, and may be in the form of either random copolymerization or block copolymerization. The repeating unit (3) and the repeating unit (4) may be contained in the A block. In this case, each repeating unit may be contained in the A block. The copolymer may be contained therein in the form of either a random copolymer or a block copolymer.

[0294] Repeating units other than repeating units (3) and (4) are contained in the A block. Examples of such repeating units include styrene, α-methylstyrene, styrene monomers such as styrene; (meth)acrylic acid chloride and other (meth)acrylates Monomers; (meth)acrylamides such as (meth)acrylamides and N-methylolacrylamides Amido monomers; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether; Croto repeating units derived from monomers such as N-methacryloylmorpholine; Units include:

[0295] The amine value of the dispersant (f1) is not particularly limited, but is preferably 20 mgKOH / g or more. , more preferably 30 mgKOH / g or more, and even more preferably 40 mgKOH / g or more; Particularly preferably 50 mgKOH / g or more, and more preferably 150 mgKOH / g or less. More preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less, It is particularly preferable that the content is 70 mgKOH / g or less. By setting the content to the lower limit or more, the NMP resistance and dispersibility are improved. By adjusting the content to the upper limit or less, the stability over time of the dispersion tends to be good. The amine value is the amount of base per gram of solid content of the dispersant (f1) and the equivalent K It is expressed as the mass of OH.

[0296] The acid value of the dispersant (f1) is not particularly limited. From the viewpoint of dispersibility, the acid value is preferably 10 mgKOH / g Preferably, the KOH content is 5 mgKOH / g or less, more preferably, 1 mgKOH / g or less. is preferred, and 0 mg KOH / g is particularly preferred.

[0297] The weight average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3,000 or more, and more preferably 5 000 or more is more preferable, 7000 or more is even more preferable, and 100000 or less is The lower limit is preferably 50,000 or less, more preferably 10,000 or less. By setting the value to be equal to or more than the upper limit, the dispersibility tends to be improved, and by setting the value to be equal to or less than the upper limit, the dispersibility tends to be improved. The stability of the dispersion over time tends to improve. In the dispersant (f1) of the present invention, the counter anion (Y - ) is present, In some cases, the weight average molecular weight cannot be measured sufficiently. In that case, - ) In some cases, the theoretical molecular weight calculated from the weight average molecular weight before mixing is used. The theoretical molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3,000 or more, and more preferably 500 or more. More preferably, it is 0 or more, even more preferably 7000 or more, and more preferably 100000 or less. The lower limit is preferably 50,000 or less, more preferably 10,000 or less. By setting the content above the upper limit, the dispersibility tends to improve, and by setting the content below the upper limit, the dispersion liquid The stability over time of the composition tends to improve.

[0298] The method for producing the dispersant (f1) is not particularly limited, and any known method can be used. For example, a precursor of the dispersant (f1) containing the repeating unit (2) is prepared, and the precursor is reacted with Then, a compound represented by the following general formula (1') is reacted to produce the compound:

[0299] [ka]

[0300] (In formula (1'), R 3 , R 4 and Y are the same as in formula (1).

[0301] The dispersant (f) in the photosensitive coloring composition of the present invention is a dispersant other than the dispersant (f1) (hereinafter Hereinafter, these may be referred to as "other dispersants."

[0302] Other dispersants include the following dispersants: From the viewpoint of dispersion stability, a carboxyl group or a base thereof; a primary, secondary or tertiary amino group; Quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine; Among them, dispersants having functional groups such as primary, secondary or tertiary amino groups; quaternary Ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine; Examples of the dispersant include a dispersant having a basic functional group. In addition, from the viewpoint that the pigment can be dispersed with a small amount of dispersant, Powders are preferred.

[0303] Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethylene dispersants, and the like. Polyallylamine-based dispersants, amino group-containing monomers and macromonomers dispersants made of mers, polyoxyethylene alkyl ether dispersants, polyoxyethylene Polyester dispersant, polyether phosphate dispersant, polyester phosphate dispersant, Examples of the dispersants include aliphatic ester dispersants and aliphatic modified polyester dispersants. Cut.

[0304] A specific example of such a polymer dispersant is EFKA (registered trademark of BASF) ), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disperlon (registered trademark Trademark. Manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark. Manufactured by Lubrizol Corporation), K P (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark) (manufactured by Soto Co., Ltd.)

[0305] Examples of urethane and acrylic polymer dispersants include DISPERBYK160~ 166, 182 series (both urethane-based), DISPERBYK2000, 200 1. BYK-LPN21116 etc. (all acrylic) (all manufactured by BYK-Chemie) ) are mentioned.

[0306] The other dispersants may be used alone or in combination of two or more.

[0307] <Other ingredients of the photosensitive coloring composition> In addition to the above-mentioned components, the photosensitive coloring composition of the present invention may contain an adhesion improving agent such as a silane coupling agent. agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, etc. Additives can be added as appropriate.

[0308] (1) Adhesion improver The photosensitive coloring composition of the present invention contains an adhesion improver in order to improve adhesion to a substrate. As the adhesion improver, a silane coupling agent, a compound containing a phosphoric acid group, etc. are preferable. stomach. Silane coupling agents include epoxy, (meth)acrylic, and amino types. Various types can be used alone or in combination of two or more.

[0309] A preferred silane coupling agent is, for example, 3-methacryloxypropylmethyldisilane. (Meth)acryloyl groups such as methoxysilane and 3-methacryloxypropyltrimethoxysilane Xysilanes, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Epoxy silanes such as silane, 3-glycidoxypropyltriethoxysilane, 3- Ureidosilanes such as 3-isocyanatepropyltriethoxysilane Examples of the isocyanate silanes include triethoxysilane and the like. Particularly preferred are epoxy silanes. It is a silane coupling agent of the xysilane family. As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphates are preferred, Preferred are those represented by the following general formula (g1), (g2) or (g3).

[0310] [ka]

[0311] In the above general formulae (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group. wherein l and l′ are integers of 1 to 10, and m is 1, 2, or 3. These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

[0312] (2) Surfactants The photosensitive coloring composition of the present invention may contain a surfactant in order to improve the coating property.

[0313] Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants. Among them, the most suitable one is the one with the lowest possibility of adversely affecting various properties. It is preferable to use a non-ionic surfactant, and among them, a fluorine-based or silicone-based surfactant is preferable. The agent is effective in terms of application properties. Such surfactants include, for example, TSF4460 (Momentive Performant). DFX-18 (manufactured by Neos), BYK-300, BYK-3 25, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicone), F- 470, F-475, F-478, F-554, F-559 (DIC), SH7PA (Toray Dow Corning), DS-401 (Daikin), L-77 (Nippon Unika Examples of such FC4430 (manufactured by 3M) include FC4430 (manufactured by 3M). The surfactant may be used alone or in any combination and ratio of two or more kinds. may be used.

[0314] (3) Pigment derivatives In the photosensitive coloring composition of the present invention, a pigment derivative is added as a dispersing aid in order to improve dispersibility and storage stability. The body may also be included. Pigment derivatives include azo, phthalocyanine, quinacridone, and benzimidazolone. , quinophthalone, isoindolinone, dioxazine, anthraquinone, indole Induction of nitrile, perylene, perinone, diketopyrrolopyrrole, dioxazine, etc. Among them, phthalocyanine-based and quinophthalone-based are preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalates, etc. Imidomethyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group, etc. Examples of such groups include those bonded directly to the base skeleton or via an alkyl group, an aryl group, a heterocyclic group, etc. A sulfonic acid group is preferable. In addition, a plurality of these substituents may be substituted on one pigment skeleton. This is also fine.

[0315] Specific examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine and sulfur derivatives of quinophthalone. anthraquinone sulfonic acid derivatives; quinacridone sulfonic acid derivatives; Examples of the sulfonic acid derivatives include diketopyrrolopyrrole and dioxazine. These may be used alone or in combination of two or more.

[0316] (4) Photoacid generator A photoacid generator is a compound that can generate acid when exposed to ultraviolet light. The acid generated during the process promotes the crosslinking reaction in the presence of crosslinking agents such as melamine compounds. Among such photoacid generators, the solubility in a solvent, particularly the photosensitive coloring composition, is particularly important. It is preferable that the solubility of the ester compound in the solvent used in the composition is high. For example, diphenyl Niliodonium, ditolyliodonium, phenyl(p-anisyl)iodonium, bi Bis(m-nitrophenyl)iodonium, Bis(p-tert-butylphenyl)iodo iodonium, bis(p-chlorophenyl)iodonium, bis(n-dodecyl)iodonium , p-isobutylphenyl(p-tolyl)iodonium, p-isopropylphenyl(p -tolyl)iodonium, or triphenylsulfonium Triarylsulfonium chlorides, bromides, or boron fluorides, Hexafluorophosphate salts, hexafluoroarsenate salts, aromatic sulfonates, Tetrakis(pentafluorophenyl)borate salts, etc., diphenylphenacylsulfonyl sulfonium organoboron complexes such as nium(n-butyl)triphenylborate; , 2-methyl-4,6-bistrichloromethyltriazine, 2-(4-methoxyphenyl Examples of triazine compounds include 1,2-dichloro-4,6-bis(trichloromethyl)triazine. This is possible, but not limited to this.

[0317] (5) Crosslinking agent The photosensitive coloring composition of the present invention may further contain a crosslinking agent, for example, melamine or As the crosslinking agent, a guanamine-based compound can be used. Examples include melamine or guanamine compounds represented by the general formula (6).

[0318] [ka]

[0319] In formula (6), R61 Ha-NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms; R 61 but- NR 66 R 67 R for group 62 , R 63 , R 64 , R 65 , R 66 and R 67 One of them is -CH2OR 68 base R 61 When R is an aryl group having 6 to 12 carbon atoms, 62 , R 63 , R 64 and R 65 One of -CH2OR 68 represents a group, R 62 , R 63 , R 64 , R 65 , R 66 and R 67 The rest are independent of each other , hydrogen or -CH2OR 68 represents a group, R 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. vinegar. Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group, or a 2- -naphthyl groups, and these phenyl and naphthyl groups can be substituted with alkyl and alkoxy groups. The alkyl group and the alkoxy group may have a substituent such as a halogen atom bonded thereto. Each of R may have about 1 to 6 carbon atoms. 68 The alkyl group represented by the formula: However, a methyl group or an ethyl group, particularly a methyl group, is preferred.

[0320] A melamine-based compound corresponding to the general formula (6), i.e., a compound of the following general formula (6-1): Hexamethylol melamine, pentamethylol melamine, tetramethylol melamine , hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethyl melamine, hexaethoxymethylmelamine, and the like.

[0321] [ka]

[0322] In formula (6-1), R 62 , R 63 , R 64 , R 65 , R 66 and R 67 If one of the groups is an aryl group, R 62 , R 63 , R 64 and R 65 One of them is -CH2OR 68 represents a group, R 62 , R 63 , R 64 , R 65 , R 66 and R 67 the remainder independently represent a hydrogen atom or -CHOR 68 represents a group, R 68 is hydrogen represents an atom or an alkyl group.

[0323] Also, a guanamine-based compound corresponding to the general formula (6), i.e., R 61 but Aryl compounds include tetramethylolbenzoguanamine, tetramethoxymethyl Benzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzo Guanamine and the like.

[0324] Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group is used. It is also possible to do this. For example: 2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl- 2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxy Methyl) perhydro-1,3,5-triazin-2-one (commonly known as N-ethyldimethylol triazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl Thiol ether, 3,5-bis(hydroxymethyl)perhydro-1,3,5-oxadiazine Azin-4-one (commonly known as dimethyloluron) or its dimethyl ether, tetramethyl Lorglyoxal diurein or its tetramethyl ether derivative.

[0325] These crosslinking agents may be used alone or in combination of two or more. The amount of the photosensitive coloring composition to be used is preferably 0.1 to 15% by mass, particularly preferably 0.1 to 15% by mass, based on the total solid content of the photosensitive coloring composition. The content is preferably 0.5 to 10% by mass.

[0326] (6) Mercapto compounds A mercapto compound is added as a polymerization accelerator and to improve adhesion to the substrate. It is also possible.

[0327] The types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercapto Benzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decane Dithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate butanediol bisthioglycolate, ethylene glycol bisthioglycolate , Trimethylolpropane tristhioglycolate, Butanediol bisthiopropionate ate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhiopropionate thioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol Sulitol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate ester, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3 -mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, Trimethylolpropane tris(3-mercaptobutyrate), Pentaerythritol tetraacetate Rakis(3-mercaptobutyrate), Pentaerythritol tris(3-mercaptobutyrate) butylate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol Rubis(3-mercaptoisobutyrate), Trimethylolpropane Tris(3-mercaptoisobutyrate) 1,3,5-Tris(3-mercaptobutyloxyethyl)-1 ,3,5-triazine-2,4,6(1H,3H,5H)-trione and other heterocyclic rings Examples of such compounds include mercapto compounds and aliphatic polyfunctional mercapto compounds. These may be used alone or in combination of two or more.

[0328] (7) Polymerization inhibitors The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of shape control. The inclusion of a polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film. It is believed that the angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled. Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and methyl hydroxypropyl ether. Hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (B Among these, from the viewpoint of shape control, 2,6-di-tert- Butyl-4-cresol is preferred. From the viewpoint of safety to the human body, hydroquinone mono is preferred. Among these, methyl ether and methylhydroquinone are preferred. It is preferable that the polymerization inhibitor contains one or more kinds. When manufacturing a resin, a polymerization inhibitor may be contained in the resin. It may be used as an inhibitor, or may contain the same or different polymerization inhibitor in addition to the polymerization inhibitor in the resin. The inhibitor may be added during the preparation of the photosensitive coloring composition.

[0329] When the photosensitive coloring composition contains a polymerization inhibitor, the content ratio of the polymerization inhibitor is not particularly limited. The total solid content of the coloring composition is usually 0.0005% by mass or more, preferably 0.001% by mass. More preferably, it is 0.01% by mass or more, and usually, it is 0.3% by mass or less, preferably The lower limit is preferably 0.2% by mass or less, and more preferably 0.1% by mass or less. By setting the value below the upper limit, the required sensitivity can be maintained. There is a tendency to be able to.

[0330] <Contents of each component in the photosensitive coloring composition> The content of the colorant (a) in the photosensitive coloring composition of the present invention is not particularly limited. The content of the photosensitive coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the photosensitive coloring composition. , more preferably 20% by mass or more, even more preferably 30% by mass or more, and 35% by mass or more More preferably, the content is 70% by mass or less, and more preferably 60% by mass or less. More preferably, the content is 50% by mass or less, and particularly preferably 45% by mass or less. By setting the content to the upper limit or less, the patterning property can be improved. tends to improve.

[0331] In addition, when the photosensitive coloring composition contains an organic coloring pigment, the content ratio thereof is not particularly limited. However, it is preferably 5% by mass or more, more preferably 20% by mass or more, based on the total solid content of the photosensitive coloring composition. It is preferably 30% by mass or more, more preferably 35% by mass or more, and more preferably 7 It is preferably 0% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting the content to the lower limit or more, the light blocking property is increased while suppressing the loss of ultraviolet light required for curing. By setting the content to the upper limit or less, the NMP resistance tends to be good.

[0332] (a) If the colorant contains red pigment and / or orange pigment, the content of red pigment and orange pigment The total proportion is not particularly limited, but it is preferably 5% by mass or more, and more preferably 8% by mass or more, in the (a) colorant. More preferably, the content is 10% by mass or more, even more preferably, 12% by mass or more is particularly preferably. , 40% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is more preferable. It is particularly preferable that the color tone is close to black by setting the color tone to be equal to or greater than the lower limit. By setting the content to the upper limit or less, high sensitivity tends to be obtained.

[0333] (a) If the coloring agent contains blue pigment and / or violet pigment, the content of blue pigment and violet pigment The total amount is not particularly limited, but it is preferably 30% by mass or more, and more preferably 50% by mass or more, in the (a) colorant. % by mass or more is more preferable, 70% by mass or more is even more preferable, and 80% by mass or more is particularly preferable. It is preferably 95% by mass or less, more preferably 92% by mass or less, and more preferably 90% by mass or less. By setting the value to be equal to or more than the lower limit, the light blocking property tends to be high. By adjusting the content to be equal to or less than the upper limit, NMP resistance tends to be good.

[0334] When the photosensitive coloring composition contains a black pigment, the content ratio of the black pigment is not particularly limited. The content of the coloring composition is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total solid content of the coloring composition. More preferably, the content is 20% by mass or more, and particularly preferably 60% by mass or less. The lower limit is preferably 50% by mass or less, more preferably 40% by mass or less. By setting the value to above the upper limit, the light blocking effect tends to be high, and by setting the value to below the upper limit, the NM P tolerance tends to be good.

[0335] In addition, when the photosensitive coloring composition contains an organic black pigment, the content ratio thereof is not particularly limited. However, the content is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total solid content of the photosensitive coloring composition. It is preferable that the content is 10% by mass or more, more preferably 20% by mass or more, and more preferably 60% by mass or more. % by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. By setting the content to be equal to or more than the lower limit, the light blocking property tends to be increased, and by setting the content to be equal to or less than the upper limit, This tends to improve NMP resistance.

[0336] When the (a) colorant contains an organic black pigment, the content ratio thereof is not particularly limited. The colorant preferably contains 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass or more. More preferably, the content is 20% by mass or more, particularly preferably 20% by mass or more, and more preferably 100% by mass or less. It is more preferably 80% by mass or less, and particularly preferably 70% by mass or less. By setting the content below the upper limit, the NMP resistance is improved. There is a tendency for it to be favorable.

[0337] In addition, when the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content The ratio is not particularly limited, but it is preferably 5% by mass or more, and more preferably 8% by mass or more in the (a) colorant. More preferably, the content is 10% by mass or more, even more preferably, 60% by mass or less, and 5 It is more preferable that the content is 0% by mass or less, and particularly preferable that the content is 40% by mass or less. In addition, by setting the value to the upper limit or less, the NMP resistance is good. There is a tendency for this to happen.

[0338] In addition, (a) when the colorant contains an organic color pigment and a black pigment, the total content of these pigments is Although not limited thereto, (a) the colorant preferably contains 30% by mass or more, and more preferably 50% by mass or more. It is preferably 70% by mass or more, more preferably 90% by mass or more. By making the content equal to or more than the lower limit, the light-shielding property tends to be improved, By adjusting the content to be equal to or less than the upper limit, NMP resistance tends to be good.

[0339] The content of the alkali-soluble resin (b) is not particularly limited. The amount of the mixture is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content of the mixture. % by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more. Usually, it is 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and Preferably 60% by mass or less, even more preferably 50% by mass or less, particularly preferably 45% by mass or less. (b) By making the content of the alkali-soluble resin equal to or more than the lower limit, This tends to suppress a decrease in the solubility of the unexposed area in a developer, thereby suppressing development defects. By adjusting the value to the upper limit or less, appropriate sensitivity can be maintained and the exposed portion can be prevented from being dissolved by the developer. In addition, there is a tendency that deterioration in the sharpness and adhesion of the pattern can be suppressed.

[0340] The content of the (b1) epoxy (meth)acrylate resin is not particularly limited, but Generally, the amount of the light-sensitive coloring composition is 10% by mass or more, preferably 20% by mass or more, based on the total solid content of the light-sensitive coloring composition. More preferably, it is 30% by mass or more, and even more preferably, it is 35% by mass or more, and usually, it is 50% by mass or more. % or less, preferably 45% or less by mass, and more preferably 40% or less by mass. By setting the temperature at or above 100° C., the solubility of the unexposed portion in the developer tends to be ensured. By setting the value to the upper limit or less, appropriate sensitivity can be maintained and dissolution of the exposed area by the developer can be suppressed. In addition, there is a tendency that deterioration in the sharpness and adhesion of the pattern can be suppressed.

[0341] (b1) Epoxy (meth)acrylate resin contained in (b) alkali-soluble resin The content is not particularly limited, but is usually 20% by mass or more, preferably 40% by mass or more, and more preferably 10% by mass or more. More preferably, it is 50% by mass or more, particularly preferably 60% by mass or more, and usually 100% by mass The content is preferably 80% by mass or more, and more preferably 70% by mass or more. By setting the above, the solubility of the unexposed portion in the developer tends to be ensured. By setting the value below the upper limit, appropriate sensitivity can be maintained and dissolution of the exposed area by the developer can be suppressed. This tends to suppress deterioration in the sharpness and adhesion of the resulting pattern.

[0342] The content of the (c) photopolymerization initiator is not particularly limited, but may be any of the following: The amount of the solid content is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more. % or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. Usually, it is 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably (c) The content of the photopolymerization initiator is set to the lower limit or more, preferably 6 mass % or less. By setting the value to the upper limit or less, the developer in the unexposed area tends to be able to suppress the decrease in sensitivity. In this case, there is a tendency that the decrease in solubility in the toner can be suppressed, and thus development defects can be suppressed.

[0343] (c) When a polymerization accelerator is used together with a photopolymerization initiator, the content ratio of the polymerization accelerator is not particularly limited. However, it is preferable that the content of the photosensitive coloring composition of the present invention is 0.05% by mass or more based on the total solid content of the photosensitive coloring composition of the present invention. The polymerization accelerator is usually 10% by mass or less, preferably 5% by mass or less. It is usually used in a ratio of 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass, per 100 parts by mass of the agent. By setting the content of the polymerization accelerator to the above lower limit or more, it is preferable that the composition is resistant to exposure light. By adjusting the value to the upper limit or less, the development of the unexposed portion tends to be suppressed. This tends to suppress the decrease in solubility in the liquid and suppress development defects. In addition, when (c) a sensitizing dye is used together with the photopolymerization initiator, the content ratio is not particularly limited. However, from the viewpoint of sensitivity, the content of the photosensitive coloring composition is usually 20% by mass or less, preferably 20% by mass or less, based on the total solid content of the photosensitive coloring composition. It is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0344] The content of the ethylenically unsaturated compound (d) is not particularly limited. The amount of the component (A) is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the composition. % by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably By making the content equal to or more than the lower limit, appropriate sensitivity can be maintained, and the exposed area can be It is possible to suppress dissolution by the developer and also to suppress deterioration of the sharpness and adhesion of the pattern. By setting the thickness to the upper limit or less, the permeability of the developer to the exposed area is increased. This tends to suppress the occurrence of the problem, making it easier to obtain a good image.

[0345] (d) Content of alkali-soluble resin (b) relative to 100 parts by mass of ethylenically unsaturated compound The ratio is usually 80 parts by mass or more, preferably 100 parts by mass or more, and more preferably 150 parts by mass or more. Preferably, the amount is 200 parts by mass or more, more preferably 250 parts by mass or more, and Usually, it is 700 parts by mass or less, preferably 500 parts by mass or less, and more preferably 400 parts by mass or less. By making the amount equal to or more than the lower limit, it is possible to obtain an appropriate amount of the adhesive without peeling. The developer tends to be dissolved and developed, and by setting the value below the upper limit, the developer is suitable. Therefore, it is possible to obtain a suitable dissolution time.

[0346] In addition, the photosensitive coloring composition of the present invention uses the (e) solvent, so that the content ratio of the total solids is The proportion is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, It is usually 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. The solution is prepared so that

[0347] The content of the dispersant (f) is not particularly limited, but is usually in the total solid content of the photosensitive coloring composition. It is 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, By making the content equal to or more than the lower limit, sufficient dispersibility tends to be obtained. By keeping the content below the upper limit, the proportion of other components is relatively reduced, improving sensitivity and plate making. This tends to suppress the decline in performance, etc.

[0348] The content of the dispersant (f1) is not particularly limited, but it is preferably in the total solid content of the photosensitive coloring composition. It is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually Usually, it is 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less. By making the content equal to or more than the lower limit, the dispersibility tends to be good. By setting the content to the upper limit or less, the voltage holding ratio tends to be high.

[0349] The content of the dispersant (f1) is not particularly limited, but is usually 10% by mass or more in the dispersant (f). It is preferably 40% by mass or more, more preferably 60% by mass or more, and more preferably 80% by mass or more. More preferably, the content is 100 mass % or less. The voltage retention rate after irradiation with ultraviolet rays increases, and NMP resistance tends to improve.

[0350] The content of the dispersant (f) relative to 100 parts by mass of the colorant (a) is usually 5 parts by mass or less. More preferably, the amount is 10 parts by mass or more, even more preferably 15 parts by mass or more, and usually 50 parts by mass or more. It is preferably 30 parts by mass or less, and more preferably 30 parts by mass or less. Dispersibility tends to be easily obtained, and by setting the content below the upper limit, the proportion of other components is relatively By reducing the amount of the photosensitive resin, the deterioration of sensitivity, plate making properties, etc. tends to be suppressed.

[0351] When the adhesion improver is used, the content ratio thereof is not particularly limited, but is preferably the total amount of the photosensitive coloring composition. The solid content is usually 0.1 to 5 mass%, preferably 0.2 to 3 mass%, and more preferably 0. By making the content of the adhesion improver equal to or more than the lower limit, the adhesion can be improved. There is a tendency that the effect can be sufficiently obtained, and the sensitivity is reduced by setting the value below the upper limit. This tends to prevent residues from remaining after development and causing defects.

[0352] In addition, when a surfactant is used, the content ratio thereof is not particularly limited, but The amount of the compound is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, based on the total solid content of the product. The content is preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass. By setting the content of the surfactant to the above lower limit value or more, the smoothness and uniformity of the coating film are easily achieved. By setting the content below the upper limit, the smoothness and uniformity of the coating film are easily achieved. There is also a tendency for deterioration of other characteristics to be suppressed.

[0353] <Physical Properties of Photosensitive Coloring Composition> The photosensitive coloring composition of the present invention has an optical density (OD) per 1 μm of coating film of 0. It is preferably 0.7 or more, and more preferably 1.0 or more. It is preferable that the ratio is 1.3 or more, and it is particularly preferable that the ratio is 1.5 or more. It is generally 4.0 or less, preferably 3.0 or less, and more preferably 2.0 or less. By making the content equal to or greater than the lower limit, sufficient light-shielding properties tend to be obtained. By setting the content to be equal to or less than the upper limit, the voltage holding ratio and NMP resistance tend to be good. The optical density (OD) per 1 μm of the coating film is The measurement can be performed using a coating film, and it is preferable to use a coating film that has been heat-cured at 230°C for 20 minutes. I wish. The optical density is the spectral sensitivity characteristic of the light receiving element according to the ISO 5-3 standard. This refers to the transmission optical density, which is expressed as visual density. It uses the A light source specified by the CIE (International Commission on Illumination). It is used to measure the transmitted optical density. For example, the X-ray measuring instrument from Sakata Inx Engineering Corporation can be used. One example is the Rite 361T(V).

[0354] <Method for producing photosensitive coloring composition> The photosensitive coloring composition of the present invention is produced in a conventional manner. Usually, (a) the colorant is mixed with paint conditioner, sand grinder, balls, etc. Dispersion treatment is performed using a mill, roll mill, stone mill, jet mill, homogenizer, etc. It is preferable that the colorant (a) is finely divided by the dispersion treatment, and therefore the coating characteristics of the resist are improved. Sexuality improves.

[0355] Dispersion processing usually involves the steps of (a) colorant, (e) solvent, and (f) dispersant, and (b) aluminum. It is preferable to use a system in which a part or all of a potassium soluble resin is used in combination (hereinafter, the dispersion treatment The composition obtained by the above process is sometimes called a "pigment dispersion liquid." In particular, (f) a highly pigmented pigment is used as a dispersant. By using a child dispersant, the thickening of the obtained pigment dispersion and photosensitive coloring composition over time is suppressed. This is preferable since it has excellent dispersion stability. In this manner, in the process for producing the photosensitive coloring composition, (a) a colorant, (e) a solvent, It is preferable to prepare a pigment dispersion that contains at least (f) a dispersant. (a) colorants, (e) solvents, and (f) dispersants that can be used in pigment dispersions The above-mentioned compounds that can be used in the photosensitive coloring composition are preferably used. In addition, the content ratio of each colorant in the pigment dispersion liquid (a) and However, the content ratio in the photosensitive coloring composition is preferably adopted. can be done.

[0356] In addition, when the dispersion treatment is performed on a liquid containing all the components to be mixed in the photosensitive coloring composition, However, the heat generated during the dispersion process may cause denaturation of highly reactive components. It is preferable to carry out the dispersion treatment in a system containing a molecular dispersant. When dispersing colorants (a) using a sand grinder, use particles of about 0.1 to 8 mm. Glass beads or zirconia beads having a diameter of 1000 mm are preferably used. The dispersion treatment conditions are as follows: temperature: The temperature is usually 0° C. to 100° C., preferably room temperature to 80° C. The dispersion time is The appropriate time varies depending on the composition and the size of the dispersion treatment device, so adjust accordingly. The composition is applied so that its 20 degree specular gloss (JIS Z8741) is in the range of 50 to 300. The purpose of dispersion is to control the gloss of the pigment dispersion. When the gloss of the photosensitive coloring composition is low, In such cases, dispersion treatment is often insufficient and coarse pigment (coloring material) particles remain, which can lead to poor developability and Adhesion, resolution, etc. may become insufficient. Also, the gloss value may not be within the above range. When the pigment is dispersed, it is crushed into a large number of ultrafine particles, which actually reduces the dispersion stability. There is a tendency for

[0357] The particle size of the pigment dispersed in the pigment dispersion is usually 0.03 to 0.3 μm. It is measured by a quantitative light scattering method. Next, the pigment dispersion obtained by the above dispersion treatment and the above-mentioned The above other components are mixed to form a uniform solution. Since fine dust may be mixed in the liquid, the obtained photosensitive coloring composition should be filtered out using a filter, etc. It is preferable to carry out filtration treatment.

[0358] [Pigment dispersion for image display devices] The pigment dispersion for an image display device of the present invention comprises (a) a colorant, (e) a solvent, and (f) a dispersant. In particular, the (a) colorant contains a black pigment, and the (f) dispersant is , containing a dispersant (f1). In the pigment dispersion liquid for an image display device of the present invention, (a) a colorant, (e) a solvent, and (f As the dispersant, those listed in the same item in the photosensitive coloring composition of the present invention are preferable. Similarly, the black pigment in the pigment dispersion liquid for the image display device of the present invention can be used. The pigment and dispersant (f1) may also be the same as those listed in the photosensitive coloring composition of the present invention. It is possible to preferably adopt those.

[0359] In the pigment dispersion liquid for an image display device of the present invention, the content ratio of the colorant (a) is not particularly limited. However, it is preferable that the content of the saturation agent is 30% by mass or more, and more preferably 50% by mass or more, based on the total solid content of the pigment dispersion. It is preferably 60% by mass or more, more preferably 80% by mass or less, and more preferably 75% by mass or less. It is more preferable that the content is 70% by mass or less, and further preferably 70% by mass or less. The voltage retention rate after ultraviolet irradiation and NMP resistance tend to be good at or above the upper limit. By adjusting the amount of the mixture to be lower than 100g, the dispersibility tends to be improved.

[0360] In the pigment dispersion liquid for an image display device of the present invention, the content ratio of the black pigment is not particularly limited. However, the content is preferably 30% by mass or more, and more preferably 50% by mass or more, based on the total solid content of the pigment dispersion. It is preferable that the content is 60% by mass or more, more preferably 80% by mass or more, and more preferably 75% by mass or more. The content is preferably 70% by mass or less, and more preferably 70% by mass or less. The voltage holding rate after irradiation and NMP resistance tend to be good, and the temperature is within the upper limit. The dispersion tends to be good.

[0361] In the pigment dispersion for an image display device of the present invention, among black pigments, The inclusion of an organic black pigment is advantageous from the viewpoint of light-shielding properties when used as a photosensitive coloring composition. It is preferable. A pigment dispersion for an image display device contains an organic black pigment represented by the general formula (1) as a black pigment. When it is contained, the content ratio is not particularly limited, but it is preferably 10% by mass or more in the (a) colorant. It is preferably 40% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more. or more is particularly preferred, and 98 mass % or more is even more particularly preferred. In the pigment dispersion liquid for an image display device of the present invention, the content ratio of the dispersant (f) is not particularly limited. However, it is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total solid content of the pigment dispersion. It is preferable that the content is 8% by mass or more, more preferably 10% by mass or more, and more preferably 35% by mass or more. % or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. It is particularly preferable that the content is 15% by mass or less. By making the content equal to or more than the lower limit, the dispersibility tends to be improved. Furthermore, by setting the value to the upper limit or less, the voltage retention rate after ultraviolet irradiation and NMP resistance are good. There is a tendency for this to happen.

[0362] In the pigment dispersion for an image display device of the present invention, the content ratio of the dispersant (f1) is not particularly limited. However, it is preferably 5% by mass or more, more preferably 8% by mass or more, based on the total solid content of the pigment dispersion. It is preferably 10% by mass or more, more preferably 35% by mass or less, and more preferably 30% by mass or less. % or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. By setting the content to the lower limit or more, the dispersibility tends to be good. By using the composition as a photosensitive coloring composition, the voltage holding rate after ultraviolet irradiation and NMP resistance are improved. tends to be favorable.

[0363] The content of the dispersant (f1) is not particularly limited, but is usually 10% by mass or more in the dispersant (f). It is preferably 40% by mass or more, more preferably 60% by mass or more, and more preferably 80% by mass or more. More preferably, the content is 100 mass % or less. When used as a photosensitive coloring composition, the voltage retention rate after ultraviolet irradiation is good, and NMP resistance is also good. Sexuality tends to improve.

[0364] In addition, the pigment dispersion liquid for an image display device of the present invention is made of a total solid by using the solvent (e). The content of the component is usually 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more. % by mass or more, and usually 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less. The solution is prepared so that the volume percentage is less than 50%.

[0365] [Cured product] A cured product can be obtained by curing the photosensitive coloring composition of the present invention. The cured product obtained by curing the color composition can be suitably used as a colored spacer.

[0366] [Colored spacer] Next, a colored spacer using the photosensitive coloring composition of the present invention will be described according to its manufacturing method. He explains.

[0367] (1) Support The material used as the support for forming the colored spacers is not particularly limited as long as it has a suitable strength. The substrate is mainly transparent, but the material may be, for example, poly Polyester resins such as ethylene terephthalate, polypropylene, polyethylene, etc. Polyolefin resin, polycarbonate, polymethyl methacrylate, polysulfone Thermoplastic resin sheets such as epoxy resin, unsaturated polyester resin, poly(meth) Examples of the material include thermosetting resin sheets such as acrylic resin sheets, and various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resin are preferable. In some cases, a transparent electrode such as O is formed on the substrate. It is also possible to do so.

[0368] The support may be corona discharged or ozone treated as necessary to improve the surface properties such as adhesion. Thin film formation of various resins such as silane coupling agents and urethane resins. You may go. The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film of various resins is formed, the thickness is usually 0.01 to 10 μm, preferably The range is preferably 0.05 to 5 μm.

[0369] (2) Colored spacers The photosensitive coloring composition of the present invention has the same functions as known photosensitive coloring compositions for color filters. It is used for the purpose of coloring spacers (black photo spacers) in the following. In the case where the photosensitive coloring composition of the present invention is used, a method for forming a black photospacer is described. This will be explained using specific examples of the law.

[0370] Usually, a photosensitive coloring composition is applied onto a substrate on which a black photospacer is to be provided. The solution is applied in a film or pattern by a cloth or other method, and the solvent is dried. A pattern is formed by a method such as photolithography, which performs imaging. By further exposing the photoresist to light or performing heat curing treatment, black photospacers are formed on the substrate. will be done.

[0371] (3) Formation of colored spacers [1] Supply method to the board The photosensitive coloring composition of the present invention is usually applied onto a substrate in a state where it is dissolved or dispersed in a solvent. The feeding method may be a conventional method such as a spinner method or a wire bar method. Coating methods include flow coating, die coating, roll coating, and spray coating. In addition, the ink can be supplied in a pattern by an inkjet method, a printing method, or the like. Among them, the die coating method can drastically reduce the amount of coating solution used and can achieve high speed. There is no effect of mist that adheres when using the smear coating method, and the generation of foreign matter is suppressed. This is preferable from a comprehensive perspective.

[0372] The amount of coating varies depending on the application. For example, in the case of black photo spacers, the dry film thickness is As the particle size, it is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm. In addition, the dry film thickness or the height of the final spacer formed is in the range of ~7 μm. It is important that the uniformity is maintained across the entire substrate. If there is a large variation, the liquid crystal panel This will result in unevenness defects in the coating.

[0373] However, the photosensitive coloring composition of the present invention can be used to produce a color having different heights by a photolithography method. When multiple black photo spacers are formed at once, the final black photo spacer The height of the spacers will be different.

[0374] As the substrate, a known substrate such as a glass substrate can be used. The surface is preferably a flat surface.

[0375] [2] Drying method After the photosensitive coloring composition is applied to the substrate, it is dried using a hot plate, an IR oven, or a co It is preferable to use a convection oven for drying. A reduced pressure drying method may also be combined, in which drying is performed in a pressure chamber.

[0376] Drying conditions should be selected appropriately depending on the type of solvent and the performance of the dryer used. The drying time depends on the type of solvent and the performance of the dryer used. The temperature is selected in the range of 40°C to 130°C for 15 seconds to 5 minutes, and preferably 50°C to 110°C. The temperature can be selected within the range of 30 seconds to 3 minutes.

[0377] [3] Exposure method The exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition. The exposure is performed by irradiating the substrate with a UV or visible light source through a turn. In this case, a method of bringing an exposure mask close to the coating film of the photosensitive coloring composition or a method of placing an exposure mask The exposure mask is placed at a position away from the coating film of the photosensitive coloring composition, and exposure light is projected through the exposure mask. Alternatively, a scanning exposure method using a laser beam without using a mask pattern may be used. In this case, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, The photopolymerization may be performed in a deoxygenated atmosphere, or by forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. After the formation of the film, exposure to light may be performed.

[0378] In a preferred embodiment of the present invention, black frames having different heights are formed by photolithography. When forming a photospacer at the same time, for example, a light-shielding part (light transmittance 0%) and multiple openings are formed. For the opening, the average light transmittance is set to 1.0, which is the opening with the highest average light transmittance (full transmission opening). An exposure mask with small openings (intermediate transmission openings) is used. The difference in the average light transmittance between the over-opening and the completely transparent opening, i.e., the difference in the exposure amount, causes a step. do. The intermediate transmission opening is, for example, a matrix-shaped light-shielding element having minute polygonal light-shielding units. There are known methods for creating the ion beam by patterning the ion beam. The absorber is made of chromium, molybdenum, etc. The light transmittance is controlled by using a film of a material such as a silicon-based material. Methods for doing so are known.

[0379] The light source used for the above exposure is not particularly limited. Examples of the light source include , 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 arc lamps, fluorescent lamps, etc. Lamp light source, argon ion laser, YAG laser, excimer laser, nitrogen laser -, helium cadmium laser, blue-violet semiconductor laser, near-infrared semiconductor laser, etc. When using a specific wavelength of light, an optical filter is used. You can also use a filter.

[0380] As for optical filters, for example, there are thin-film types that can control the light transmittance at the exposure wavelength. In that case, the material may be, for example, a Cr compound (Cr oxide, nitride, oxynitride, etc.) Examples include MoSi, Si, W, and Al.

[0381] The exposure dose is usually 1 mJ / cm 2 More than 5mJ / cm, preferably 5mJ / cm 2 More than that, more preferred Or 10mJ / cm 2 More than 300 mJ / cm 2 Less than 200mJ, preferably / cm 2 Less than or equal to 150 mJ / cm 2 The following is the result. In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 1 0 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.

[0382] [4] Development method After the above exposure, the film is developed using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution can further contain a surfactant. , organic solvents, buffers, complexing agents, dyes or pigments.

[0383] Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, and charcoal. Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate , potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, phosphorus Sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate Inorganic alkaline compounds such as ammonium hydroxide, mono-, di- or triethanolamine Amines, mono-, di- or trimethylamines, mono-, di- or triethylamines, No- or diisopropylamine, n-butylamine, mono-, di- or triisopropanoic acid amine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxyl These alkaline compounds include organic alkaline compounds such as trimethylammonium hydroxide (TMAH) and choline. The compound may be a mixture of two or more types.

[0384] Examples of the surfactant include polyoxyethylene alkyl ethers, ... Diethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sol Nonionic surfactants such as pentane alkyl esters and monoglyceride alkyl esters Detergents; alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl Anionic interfaces such as sulfates, alkylsulfonates, and sulfosuccinates Surfactants: amphoteric surfactants such as alkyl betaines and amino acids.

[0385] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, and ethyl acetate. Rosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone Alcohols and other organic solvents can be used alone or in combination with an aqueous solution. Good too.

[0386] There are no particular limitations on the conditions of the development process. Usually, the development temperature is in the range of 10 to 50°C, and preferably 15 The developing method is preferably a dipping developing method, a spray developing method, or the like. This can be achieved by any method such as a brush development method or an ultrasonic development method.

[0387] [5] Post-exposure and heat-curing treatment After development, the substrate may be exposed to light in the same manner as described above, if necessary. The heat curing treatment conditions are a temperature of 100° C. to 200° C. The temperature is selected within the range of 80°C, preferably within the range of 150°C to 250°C, and the time is selected within the range of 5 minutes to 60 minutes. is selected within the range.

[0388] The size and shape of the colored spacer of the present invention depend on the specifications of the color filter to which it is applied. The photosensitive coloring composition of the present invention is particularly suitable for photolithography. By using this method, black photo spacers with different heights of spacer and sub-spacer are simultaneously In this case, the height of the spacer is usually about 2 to 7 μm. The sub-spacer usually has a height that is lower than the spacer by about 0.2 to 1.5 μm. In addition, the optical density (OD) per 1 μm of the colored spacer of the present invention is It is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. It is usually 4.0 or less, and preferably 3.0 or less. Here, the optical density (OD) is The values ​​were measured using the method described below.

[0389] [Bulkhead] The photosensitive coloring composition of the present invention is preferably used for partition walls, particularly for partition walls for dividing organic layers of an organic electroluminescent device. It can be suitably used for forming a wall. For example, a hole injection method as described in JP 2016-165396 A is used. Examples of such an organic layer include an organic layer used as a hole transport layer on a hole injection layer, a hole transport layer on a hole injection layer, and the like. Next, the partition wall using the photosensitive color composition of the present invention will be described according to its manufacturing method. do.

[0390] (1) Support The support and substrate for forming the partition wall are the above-mentioned colored spacers. The same supports and substrates as those for the above-mentioned can be used.

[0391] (2) Bulkhead In the following, when the photosensitive coloring composition of the present invention is used as a partition wall, A specific example of the formation method will be described below.

[0392] Generally, a photosensitive coloring composition is applied in the form of a film on a substrate on which the partition wall is to be formed by a method such as coating. Alternatively, the solution is supplied in a pattern, and the solvent is dried. The pattern is formed by a method such as the roughening method. After that, additional exposure or heat curing treatment is performed if necessary. By carrying out the process, partition walls are formed on the substrate.

[0393] (3) Formation of partitions In the method for forming partition walls using the photosensitive coloring composition of the present invention, Specific methods for supplying the material, drying, exposing, developing, additional exposure and heat curing are as follows: The same method as for forming the colored spacers described above can be used.

[0394] When the present invention is used as a partition wall, the size, shape, etc. depend on the organic electroluminescent device to which it is applied. Although it is appropriately adjusted depending on the specifications of the child, the partition wall formed from the photosensitive coloring composition of the present invention The height is usually about 0.5 to 10 μm. From the viewpoint of light-shielding property, the optical density (OD) per 1 μm of the partition wall of the present invention is as follows: Preferably 0.7 or more, more preferably 1.2 or more, even more preferably 1.5 or more, 1. It is particularly preferably 8 or more. It is usually 4.0 or less, and preferably 3.0 or less. The optical density (OD) here is a value measured by the method described below.

[0395] [Organic electroluminescent device] The organic electroluminescent device of the present invention is a cured product, for example, a separator, which is made of the above-mentioned photosensitive coloring composition. Equipped with walls. For example, various types of substrates having a partition wall pattern manufactured by the above-described method can be used. The organic electroluminescent device is manufactured by the method of forming the organic electroluminescent device. However, preferably, after forming a pattern of partition walls on a substrate by the above method, a functional material is applied to the substrate. A deposition method in which the material is sublimated in an empty state and deposited in an area surrounded by a partition on a substrate to form a film; Pixels are printed using wet processes such as casting, spin coating, and inkjet printing. By forming the organic layers such as the above, an organic electroluminescent device is manufactured.

[0396] There are two types of organic electroluminescent devices: bottom emission and top emission. Some examples include: In the bottom emission type, for example, a partition is formed on a glass substrate on which transparent electrodes are laminated. The hole transport layer, the light emitting layer, the electron transport layer, and the metal electrode layer are laminated in the opening surrounded by the partition wall. On the other hand, in the case of top emission type, for example, a metal electrode layer is laminated on a glass substrate. A partition is formed on the substrate, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are formed in an opening surrounded by the partition. It is created by stacking the above. The light-emitting layer may be formed by using the method described in JP-A-2009-146691 or JP-A-5734681. In addition, the organic electroluminescent layer described in Japanese Patent No. 5653387 Quantum dots such as those described in Japanese Patent No. 5,653,101 may also be used. .

[0397] The layer structure is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may be formed from a viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but the thickness may be determined based on the light emission efficiency and brightness. In terms of the degree of reflection, it is usually 1 to 500 nm.

[0398] The organic electroluminescent device may be formed with each of the RGB colors being separated for each opening, or may be formed with a single opening. Two or more colors may be laminated on the opening. The sealing layer prevents moisture in the air from being adsorbed to the organic electroluminescent device, thereby improving the light emission efficiency. In addition, the organic electroluminescent device has a function of preventing a decrease in light extraction efficiency. From the viewpoint of the antireflection effect, a low reflection film may be provided at the interface with air. By placing the material in the same position, the refractive index gap can be reduced, and it is expected that reflection at the interface can be suppressed. Such low reflection films include technologies such as moth-eye structures and super multi-layer films.

[0399] When the organic electroluminescent device is used as a pixel of an image display device, the light-emitting layer of a pixel It is necessary to prevent light from leaking to other pixels, and if the electrodes are made of metal, In order to prevent deterioration of image quality due to reflection of external light, it is necessary to form an organic electroluminescent device. It is preferable to provide the partition walls with a light-shielding property. In addition, in an organic electroluminescent device, it is necessary to provide electrodes on the upper and lower surfaces of the partition wall. Therefore, from the viewpoint of insulation, it is preferable that the partition has a high resistance and a low dielectric constant. Therefore, when a colorant is used to impart light-shielding properties to the partition walls, the colorant should have high resistance and low dielectric constant. It is preferable to use the organic pigments mentioned above.

[0400] [Image display device] The image display device of the present invention comprises the above-mentioned cured product of the present invention. For example, an alignment film is formed on a liquid crystal driving substrate (array substrate) having the colored spacers of the present invention. A liquid crystal cell is formed by bonding the counter electrode substrate to the counter electrode substrate, and liquid crystal is injected into the liquid crystal cell. Thus, an image display device such as a liquid crystal display device is manufactured, which is provided with the colored spacer of the present invention. can be done. On the other hand, the colored spacer of the present invention is disposed on the counter electrode substrate side, and the liquid crystal driving substrate (array substrate) The present invention can also be achieved by laminating the substrate and the substrate together to form a liquid crystal cell, and then injecting liquid crystal into the liquid crystal cell. It is possible to manufacture an image display device such as a liquid crystal display device having the colored spacers. In addition, for example, as described in JP 2014-215614 A, By using a substance to inject liquid crystal into a liquid crystal cell and then irradiating it with ultraviolet light, the liquid crystal alignment can be improved. It can be done. EXAMPLES

[0401] Next, the present invention will be described in more detail with reference to examples and comparative examples. As long as the amount does not exceed the range, the present invention is not limited to the following examples. Constituents of the pigment dispersions and photosensitive coloring compositions used in the following Examples and Comparative Examples, and The evaluation methods are as follows.

[0402] <Alkali-soluble resin-I> 145 parts by mass of propylene glycol monomethyl ether acetate was added while replacing with nitrogen. The mixture was stirred and heated to 120° C. 10 parts by mass of styrene and 8 parts by mass of glycidyl methacrylate were added thereto. 5.2 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA 66 parts by mass of 2,2'-azobis-2-methylbutyronitride was then dropped into the flask. 8.47 parts by mass of ethanol was added dropwise over 3 hours, and the mixture was further stirred at 90°C for 2 hours. The inside of the vessel was replaced with air, and 43.2 parts by mass of acrylic acid was mixed with tris(dimethylaminomethyl)phenol. Add 0.7 parts by mass of alcohol and 0.12 parts by mass of hydroquinone and react at 100°C for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA), triethyl 0.7 parts by mass of amine was added and reacted at 100° C. for 3.5 hours. The weight average molecular weight Mw of the soluble resin-I measured by GPC is 8400, and the acid value is 80 mg KOH / g.

[0403] <Alkali-soluble resin-II> Nippon Kayaku Co., Ltd. "XD1000" (polyglycerol of dicyclopentadiene-phenol polymer) 300 parts by weight of epoxy equivalent 252, 87 parts by weight of acrylic acid, p-methacrylate 0.2 parts by mass of oxyphenol, 5 parts by mass of triphenylphosphine, and propylene glycol 255 parts by mass of methyl ether acetate was charged into a reaction vessel, and the acid value was measured at 100°C. The mixture was stirred until the mixture was 3.0 mgKOH / g. Then, 145 g of tetrahydrophthalic anhydride was added. parts by mass were added and reacted at 120° C. for 4 hours. The weight average molecular weight Mw of II measured by GPC was 2600, and the acid value was 106 mgKOH / It was g.

[0404] <Pigment-I> CI Pigment Blue 60 <Pigment-II> CI Pigment Orange 64 <Pigment-III> CI Pigment Violet 29 <Pigment-IV> BASF Irgaphor (registered trademark) Black S 0100 CF. The organic black pigment has a chemical structure represented by the general formula (2).

[0405] [ka]

[0406] <Dispersant-I> A block containing a repeating unit having a solvent-philic group and a repeating unit having a pigment-adsorbing group A methacrylic ABA triblock copolymer having a B block containing the following formula (a): It has a repeating unit of ~(g). The amine value is 61 mg KOH / g. The theoretical molecular weight is 8,600 and has a repeating unit represented by general formula (1).

[0407] The content ratio of the repeating units of the following formulae (a) to (g) in all repeating units is (a) 40.4 mol%, (b) 13.8 mol%, (c) 9.2 mol%, (d) 7.6 mol%. mol%, (e) 2.7 mol%, (f) 17.1 mol%, and (g) 9.2 mol%.

[0408] [ka]

[0409] [ka]

[0410] <Dispersant-II> A block containing a repeating unit having a solvent-philic group and a repeating unit having a pigment-adsorbing group A methacrylic ABA triblock copolymer having a B block containing the following formula (a): It has a repeating unit of ~(g). The amine value is 66 mg KOH / g. The theoretical molecular weight is 8,600, and does not have a repeating unit represented by general formula (1).

[0411] The content ratio of the repeating units of the following formulae (a) to (g) in all repeating units is (a) 40.4 mol%, (b) 13.8 mol%, (c) 9.2 mol%, (d) 7.6 mol%. mol%, (e) 2.7 mol%, (f) 17.1 mol%, and (g) 9.2 mol%.

[0412] [ka]

[0413] [ka]

[0414] <Solvent-I> PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II> MB: 3-methoxy-1-butanol

[0415] <Photopolymerization initiator-I> Oxime ester photoinitiator with the following chemical structure:

[0416] [ka]

[0417] <Photopolymerization initiator-II> Oxime ester compounds with the following chemical structure: (4-Acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazone) 3-[3-[4-oxopentanoic acid methyl]carbazol-3-yl)

[0418] [ka]

[0419] <Ethylenically unsaturated compounds> DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Surfactant> DIC Megafack F-559 <Additives> Nippon Kayaku Co., Ltd. KAYAMER PM-21 (phosphate containing methacryloyl group)

[0420] <Evaluation of Viscosity> The viscosity of the prepared pigment dispersion was measured using a Toki Sangyo RE-85L viscometer (measurement conditions: 23 ℃, 20 rpm).

[0421] <Measurement of optical density per unit film thickness (unit OD value)> The optical density per unit film thickness was measured by the following procedure. First, the prepared photosensitive coloring composition was spin coated so that the film thickness after heat curing was 3.0 μm. Apply the mixture to a glass substrate using a coater, dry it under reduced pressure for 1 minute, and then heat it on a hot plate at 90°C. The resulting coating film was exposed to light without using an exposure mask. The irradiation light source has an intensity of 45 mW / cm at a wavelength of 365 nm. 2 Using high pressure mercury lamps, The exposure dose is 50 mJ / cm 2 Then, it was heated and cured in an oven at 230℃ for 20 minutes. Thus, a resist-coated substrate 1 was obtained. The optical density (OD value) of the obtained resist-coated substrate 1 was measured using an X-Rite 361T(V) Transmission densitometer (color temperature of illumination light source: approx. 2850K (equivalent to CIE standard illuminant A), spectral Sensitivity characteristics: Measured using ISO visual density according to ISO 5-3 standard The thickness was measured using a non-contact surface / layer cross-sectional shape measurement system, VertScan, manufactured by Ryoka Systems Co., Ltd. (R) 2.0, and the optical density (OD value) and film thickness are used to calculate the film thickness per unit film thickness (1 μm). The optical density (unit: OD value) of the sample was calculated. The OD value is a value that indicates the light-shielding ability. The higher the value, the higher the light-blocking ability.

[0422] <Evaluation of voltage holding ratio (VHR) and ion density> An empty cell was prepared by the method described in WO 2018 / 151079. Liquid crystal (MLC-6608, manufactured by Merck Japan) was poured into the empty cell obtained, and the periphery was The liquid crystal cell was sealed with a UV-curable sealant. The liquid crystal cell was then annealed (in a hot air circulating oven). The mixture was heated at 105°C for 2.5 hours to prepare a liquid crystal cell for measurement.

[0423] The liquid crystal cell we created was subjected to a voltage of 5V, 0.6Hz, and a frame time of 1667msec. Voltage was applied under the conditions and ultraviolet light was irradiated using a Toyo Corporation "Liquid Crystal Property Evaluation Device - 6254 Model." The voltage retention rate was measured. The voltage retention rate is an index of electrical reliability. The higher the better. Then, using the same device, apply a triangular wave of 0.1Hz and ±3V to the liquid crystal cell for measurement. The current was measured over time when the impurity ions were applied, and the waveform of the current change over time was obtained. The area of ​​the ion peak was measured to determine the ion density (pC) before UV irradiation.

[0424] Next, the liquid crystal cell for measurement was exposed to a high-pressure mercury lamp at 18 J / cm 2 , illuminance 40mW / cm 2 In ultraviolet The liquid crystal cell for measurement after the ultraviolet irradiation was then irradiated with ultraviolet light in the same manner as described above. The voltage retention rate after irradiation and the ion density after ultraviolet irradiation were measured.

[0425] <NMP Resistance Evaluation> The N-methylpyrrolidone (NMP) resistance evaluation was performed according to the following procedure. First, the prepared photosensitive coloring composition was applied to an IZO substrate with a spin coater so that the film thickness after heat curing would be 3.0 μm, and after drying under reduced pressure for 1 minute, it was dried on a hot plate at 90 °C for 140 seconds. for 140 seconds. The obtained coating film was exposed without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp with an intensity of 45 mW / cm² at a wavelength of 365 nm was used, and the exposure dose was 50 mJ / cm². As the irradiation light source, a high-pressure mercury lamp with an intensity of 45 mW / cm² at a wavelength of 365 nm was used, and the exposure dose was 50 mJ / cm². 2 As the irradiation light source, a high-pressure mercury lamp with an intensity of 45 mW / cm² at a wavelength of 365 nm was used, and the exposure dose was 50 mJ / cm². As the irradiation light source, a high-pressure mercury lamp with an intensity of 45 mW / cm² at a wavelength of 365 nm was used, and the exposure dose was 50 mJ / cm². 2 Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. Subsequently, a developer solution composed of an aqueous solution containing 0.05 mass% potassium hydroxide and 0.08 mass% nonionic surfactant ("A-60" manufactured by Kao Corporation) was used, and shower development was performed at 25 °C with a water pressure of 0.05 MPa. A halogen lamp and a deuterium lamp (switching wavelength 360 nm) were used, and the detector was The measurement conditions were a slit width of 2 nm. The MP elution solution was placed in a 1 cm square quartz cell and measured. It is a dimensionless quantity that indicates the degree to which the light intensity is attenuated when light passes through an object, and is expressed as follows: It is defined by the formula:

[0426] A(absorbance)=-log 10 (I / I0) (I: transmitted light intensity, I0: incident light intensity)

[0427] In addition, when light was irradiated from the same light source onto the sample solution and onto the NMP solution alone, The light intensity transmitted through the liquid can be regarded as I0, and the light intensity transmitted through the sample solution as I. Therefore, (I / I0) in the above formula represents the light transmittance, and the absorbance A is the The absorbance A is the logarithmic expression of the reciprocal of the concentration of the substance contained in the sample solution. This is the notation used when calculating absorbance, etc. When absorbance A=0, no light is absorbed. When the absorbance A is ∞, no light is transmitted. (0% transmittance). In other words, the higher the absorbance, the more the resist coating components A large amount of eluted in NMP, indicating poor NMP resistance. The spectral area was calculated and the NMP resistance was evaluated according to the following criteria. The spectral area of ​​the absorbance can be expressed as the sum of the absorbance at each wavelength, and the amount of eluted resist can be calculated. It means the sum of the components.

[0428] NMP resistance evaluation criteria: Judgment based on the spectral area value of absorbance (wavelength 300 to 800 nm ) A: 70 or less B: Over 70 and under 100

[0429] <Preparation of pigment dispersions 1 to 3> The pigment, dispersant, alkali-soluble resin, and solvent shown in Table 1 were mixed in the mass ratios shown in Table 1. The mixture was stirred in a paint shaker at 25 to 45°C for 3 hours. The beads used were zirconia beads with a diameter of 0.5 mm, and the dispersion liquid After dispersion was completed, the beads and the dispersion liquid were separated using a filter. Pigment dispersions 1 and 2 were prepared. The amount of solvent in Table 1 includes the amount of solvent derived from the dispersant and the alkali-soluble resin. The evaluation results of the viscosity of the pigment dispersion liquid measured by the above-mentioned method are shown in Table 1.

[0430] [Table 1]

[0431] [Examples 1 and 2 and Comparative Example 1] Each component was mixed so that the solid content of each component in the total solid content was the value shown in Table 2. Then, PGMEA was added so that the total solid content was 22% by mass, and the mixture was stirred and dissolved. The photosensitive coloring compositions of Examples 1 and 2 and Comparative Example 1 were prepared by dissolving the above-mentioned mixture. The evaluation results of unit OD value, voltage holding ratio (VHR), ion density, and NMP resistance measured by The results are shown in Table 2.

[0432] [Table 2]

[0433] From Table 2, it can be seen that the photosensitive coloring composition of Comparative Example 1 has insufficient ion density after ultraviolet irradiation. On the other hand, the photosensitive coloring composition of Example 1 exhibited good voltage retention and ion density after ultraviolet irradiation. It was good. The dispersant-II used in the photosensitive coloring composition of Comparative Example 1 has an ammonium group. A phenylmethyl group is bonded to the nitrogen atom, but this bond is broken by exposure to ultraviolet light. It is easy to form phenylmethyl radicals and exist in the liquid crystal, which deteriorates the ion density. In contrast, the dispersant (f 1) is R in formula (I) 4 is a naphthyl group, i.e., a polycyclic aromatic hydrocarbon group. The aromatic hydrocarbon group absorbs ultraviolet light, so the bond formed by ultraviolet light irradiation is It is believed that the breakage was suppressed, and the voltage holding ratio and ion density were improved.

[0434] The photosensitive coloring composition of Example 2 also contains the dispersant (f1), and the voltage holding ratio, It is believed that the on density has improved.

[0435] In addition, compared to the photosensitive coloring composition of Comparative Example 1, the photosensitive coloring compositions of Examples 1 and 2 had a higher N The MP resistance was also good. Dispersant-II used in the photosensitive coloring composition of Comparative Example 1 As mentioned above, a phenylmethyl group is bonded to the nitrogen atom that constitutes the ammonium group. Because these dispersants are not highly hydrophobic, they dissolve easily in NMP, and impurities in the pigment are also easily dissolved. It is presumed that a large amount was dissolved in NMP. The dispersant (f1) is, as described above, R 4 is a polycyclic aromatic hydrocarbon group The dispersant (f1) itself is difficult to dissolve in NMP, and as a result, the surface It is assumed that impurities in the material are also less likely to dissolve into NMP.

Claims

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

2. A photosensitive coloring composition comprising: (a) a colorant; (b) an alkali-soluble resin; (c) a photopolymerization initiator; (d) an ethylenically unsaturated compound; (e) a solvent; and (f) a dispersant, The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more, The photosensitive coloring composition, characterized in that the (f) dispersant contains a dispersant (f1) having a repeating unit represented by the following general formula (1), and the amine value of the dispersant (f1) is 30 mg KOH / g or more. 【Chemistry 2】 In formula (1), R 1 and R 2 each independently represent an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R 1 and R 2 may be bonded to each other to form a cyclic structure. R 3 is an alkylene group. R 4 is a polycyclic aromatic hydrocarbon group which may have a substituent. R 5 is a hydrogen atom or a methyl group. X is a divalent linking group. Y is a halogen atom.

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

4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the colorant (a) includes a black pigment.

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

6. The photosensitive coloring composition according to any one of claims 1 to 5, which is for forming a colored spacer.

7. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 6.

8. An image display device comprising the cured product according to claim 7.

9. A pigment dispersion for an image display device, comprising: (a) a colorant; (e) a solvent; and (f) a dispersant, The (a) colorant contains a black pigment, A pigment dispersion for an image display device, wherein the (f) dispersant contains a dispersant (f1) having a repeating unit represented by the following general formula (1): 【Chemistry 3】 (In formula (1), R １ and R ２ each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent; R １ and R ２ may be bonded to each other to form a ring structure. R ３ is an alkylene group. R ４ is a polycyclic aromatic hydrocarbon group which may have a substituent, and the polycyclic aromatic hydrocarbon group has two or more aromatic rings. R ５ is a hydrogen atom or a methyl group. X is a divalent linking group. Y is a halogen atom.

10. A pigment dispersion for an image display device, comprising: (a) a colorant; (e) a solvent; and (f) a dispersant, The (a) colorant contains a black pigment, The pigment dispersion liquid for an image display device, wherein the (f) dispersant contains a dispersant (f1) having a repeating unit represented by the following general formula (1), and the amine value of the dispersant (f1) is 30 mgKOH / g or more: 【Chemistry 4】 In formula (1), R 1 and R 2 each independently represent an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R 1 and R 2 may be bonded to each other to form a cyclic structure. R 3 is an alkylene group. R 4 is a polycyclic aromatic hydrocarbon group which may have a substituent. R 5 is a hydrogen atom or a methyl group. X is a divalent linking group. Y is a halogen atom.

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