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

Abstract

The present invention provides a photosensitive colored resin composition which can reduce the generation of smoke during firing and has an excellent residual film rate after firing. This photosensitive colored resin composition contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated compound, and is characterized in that: the alkali-soluble resin (C) contains a specific polyamideimide (meth) acrylate resin (C-1) and an alkali-soluble resin other than the polyamideimide (meth) acrylate resin (C-1); the cured coating film has an optical density of 0.5 or more per 1 [mu] m film thickness.

Description

Technical Field

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

[0002] This application claims priority based on Japanese Patent Application No. 2022-194625 filed in Japan on December 6, 2022, and the contents are incorporated herein by reference. Background Art

[0003] Liquid crystal displays (LCDs) utilize the property that the arrangement of liquid crystal molecules is switched by turning on / off a voltage applied to liquid crystals. On the other hand, the components constituting an LCD unit are often formed by methods using photosensitive compositions, such as photolithography.

[0004] The photosensitive composition has a further widened application range because of the fact that it is easy to form a fine structure and to handle substrates for large screens.

[0005] Image display devices including organic electroluminescent elements (also called organic electroluminescence, organic EL) have excellent visual recognition and responsiveness such as contrast and viewing angle, and can achieve low power consumption, thinness and lightness, and flexibility of the display body. Therefore, they are attracting attention as the next generation of flat panel displays (FPD).

[0006] The organic electroluminescent element has a structure in which an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes at least one of which is light-transmissive. The image display device displays images by driving a panel in which the organic electroluminescent element is arranged for each pixel.

[0007] Conventionally, such an organic electroluminescent element is manufactured by forming a bank on a substrate and then laminating a light-emitting layer or various functional layers in a region surrounded by the bank.

[0008] In order to form a light-emitting layer or the like in a region surrounded by the partition walls, a vapor deposition method is mainly used in which a material is sublimated in a vacuum state and attached to a substrate to form a film.

[0009] In recent years, methods of forming films using wet processes such as cast film, spin coating, and inkjet printing have attracted attention. In particular, inkjet printing can reduce uneven film thickness when forming a large area, and can achieve high-definition displays based on coating, reduce the amount of material used, and improve the yield rate. Therefore, it is suitable as a film forming method for organic layers in large panels.

[0010] As a method for easily forming the partition wall, a method of forming the partition wall by photolithography using a photosensitive composition is known. In addition, as a method for providing the partition wall with light-shielding properties to suppress light leakage between pixels, a method of adding a colorant to the photosensitive composition is known.

[0011] Patent Document 1 describes a colored photosensitive resin composition which is effective in suppressing the generation of outgassing by using a specific organic black pigment and an alkali-soluble resin and can be used for partition walls of an organic electroluminescent element.

[0012] In addition, Patent Document 2 describes the use of a solder resist having excellent heat resistance and development solubility by using a specific polyamide-imide resin. Furthermore, Patent Document 3 describes a photosensitive composition for use in color filters that is effective in brightness, contrast, and water stain suppression after development by using a specific polyamide-imide resin.

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: International Publication No. 2018 / 101314

[0016] Patent Document 2: International Publication No. 2020 / 075994

[0017] Patent Document 3: International Publication No. 2017 / 146426 Summary of the invention

[0018] Problems to be solved by the invention

[0019] In the photosensitive colored resin composition used for the light-shielding partition application, depending on the structure of the alkali-soluble resin, it is sometimes thermally decomposed during firing to generate smoke. In addition, if a colorant is contained in the composition in order to ensure light-shielding properties, the photopolymerizable component is reduced and light is shielded, so the photocuring inside the film becomes insufficient. Therefore, sometimes unreacted low-molecular components are generated as smoke from the inside of the film during firing. As a result, the generated smoke components adhere to the anode, which may cause the drive voltage of the element to rise, the uneven display of the light-emitting surface, etc. In addition, there is a tendency that the element current density is low relative to the applied voltage, and sometimes sufficient brightness cannot be obtained.

[0020] In addition, when the residual film rate of the photosensitive color resin composition is low, it is likely to be affected by fluctuations in the development step and the firing step during the production of the barrier ribs, and the production quality may become unstable.

[0021] The present inventors have conducted studies and found that the partition walls formed from the colored photosensitive composition described in Patent Document 1 do not sufficiently reduce the amount of smoke generated during firing.

[0022] On the other hand, in the photosensitive compositions described in Patent Documents 2 and 3, when a colorant is contained in order to ensure light-shielding properties, the residual film ratio after firing is insufficient.

[0023] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring resin composition which can reduce the generation of smoke during firing and has an excellent residual film ratio after firing.

[0024] Another object of the present invention is to provide a cured product obtained by curing a photosensitive colored resin composition; a partition wall formed of the cured product; an organic electroluminescent element and an image display device having the partition wall, suppressing an increase in driving voltage and having excellent display reliability.

[0025] Means for solving problems

[0026] The present inventors have conducted intensive studies and, as a result, have found that the above-mentioned problems can be solved by using a specific alkali-soluble resin in a photosensitive coloring resin composition, thereby completing the present invention.

[0027] That is, the gist of the present invention is as follows.

[0028] [1] A photosensitive colored resin composition comprising (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated compound,

[0029] The alkali-soluble resin (C) contains a polyamideimide (meth)acrylate resin (C-1),

[0030] The polyamideimide (meth)acrylate resin (C-1) is a resin obtained by reacting a compound (C-1-2), a compound (C-1-3) and a polyamideimide resin (C-1-1).

[0031] The polyamide-imide resin (C-1-1) is a polyamide-imide resin having a terminal acid group or anhydride group obtained by reacting a compound (C-1-11) with a compound (C-1-12).

[0032] The aforementioned compound (C-1-11) is an isocyanurate type polyisocyanate,

[0033] The aforementioned compound (C-1-12) is a tricarboxylic anhydride,

[0034] The aforementioned compound (C-1-2) is a (meth)acrylate having an epoxy group in the molecule.

[0035] The aforementioned compound (C-1-3) is a dicarboxylic anhydride and / or a tricarboxylic anhydride,

[0036] The alkali-soluble resin (C) further contains an alkali-soluble resin other than the polyamideimide (meth)acrylate resin (C-1),

[0037] The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more.

[0038] [2] The photosensitive colored resin composition according to [1], wherein the (A) colorant contains an organic pigment.

[0039] [3] The photosensitive colored resin composition according to [2], wherein the organic pigment contains an organic black pigment.

[0040] [4] The photosensitive colored resin composition according to [3], wherein the organic black pigment contains a benzodifuranone-based organic black pigment.

[0041] [5] The photosensitive colored resin composition according to [4], wherein the benzodifuranone-based organic black pigment contains at least one organic black pigment selected from the group consisting of a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, and a salt of a geometric isomer thereof.

[0042] [Chemistry 1]

[0043]

[0044] (In formula (A-1-1), R 611 and R 616 Each independently represents a hydrogen atom, CH 3 CF 3 , fluorine atom or chlorine atom; R 612 , R 613 , R 614 , R 615 , R 617 , R 618 , R 619 and R 620 Each independently represents a hydrogen atom, a halogen atom, R 621 、COOH、COOR 621 、COO - ,CONH 2 ,CONHR 611 ,CONR 621 R 622 、CN、OH、OR 621 、COCR 621 、OOCNH 2 ,OOCNHR 621 、OOCNR 621 R 622、NO 2 NH 2 、NHR 621 NR 621 R 622 、NHCOR 622 NR 621 COR 622 、N=CH 2 、N=CHR 621 、N=CR 621 R 622 , SH, SR 621 , SOR 621 、SO 2 R 621 、SO 3 R 621 、SO 3 H.SO 3 - 、SO 2 NH 2 、SO 2 NHR 621 or SO 2 NR 621 R 622 ; Select from R 612 and R 613 , R 613 and R 614 , R 614 and R 615 , R 617 and R 618 , R 618 and R 619 and R 619 and R 620 At least one of the groups may be directly bonded to each other, or may be bonded to each other through an oxygen atom, a sulfur atom, NH or NR 621 Bridge and bond to each other; R 621 and R 622 Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.)

[0045] [6] The photosensitive color resin composition according to any one of [1] to [5], wherein the content of the colorant (A) is 10% by mass or more relative to the total solid content of the photosensitive color resin composition.

[0046] [7] The photosensitive colored resin composition according to any one of [1] to [6], wherein the alkali-soluble resin (C) contains an epoxy (meth)acrylate resin (C-2) having an aromatic ring in its main chain as the alkali-soluble resin other than the polyamideimide (meth)acrylate resin (C-1).

[0047] [8] The photosensitive colored resin composition according to any one of [1] to [7], wherein the content of the polyamideimide (meth)acrylate resin (C-1) in the (C) alkali-soluble resin is 10% by mass or more and 90% by mass or less.

[0048] [9] The photosensitive colored resin composition according to any one of [1] to [8], wherein the content of the (C) alkali-soluble resin is 100 parts by mass or more relative to 100 parts by mass of the (E) ethylenically unsaturated compound.

[0049]

[10] The photosensitive colored resin composition according to any one of [1] to [9], which is used for forming a partition wall.

[0050]

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

[10] .

[0051]

[12] A partition wall formed of the cured product described in

[11] .

[0052]

[13] An organic electroluminescent element comprising the partition wall described in

[12] .

[0053]

[14] A color filter having the partition wall described in

[12] and containing light-emitting nanocrystals.

[0054]

[15] An image display device comprising the partition wall described in

[12] .

[0055] Effects of the Invention

[0056] According to the present invention, it is possible to provide a photosensitive color resin composition which can reduce smoke generation during firing and has an excellent residual film ratio after firing. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] [ Figure 1 ] Figure 1 This is a schematic cross-sectional view of an example of a color filter including the partition wall of the present invention. DETAILED DESCRIPTION

[0058] Hereinafter, although embodiment of the present invention is specifically described, the present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist thereof.

[0059] In the present invention, the following terms have the following meanings.

[0060] The numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0061] “(Meth)acrylic acid” means “either or both of acrylic acid and methacrylic acid”, and the same applies to “(meth)acrylate” and “(meth)acryloyl”.

[0062] In the present invention, the "acrylic resin" refers to a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylate having a carboxyl group.

[0063] The term "(co)polymer" includes both homopolymers and copolymers.

[0064] "Acid (anhydride)" and "...acid (anhydride)" include both an acid and its anhydride.

[0065] The term "monomer" is used in contrast to a so-called high molecular substance (polymer), and means that in addition to a monomer in a narrow sense, it also includes dimers, trimers, and oligomers.

[0066] The “total solid content” refers to all components other than the solvent contained in the photosensitive color resin composition or the pigment dispersion. Even if components other than the solvent are liquid at room temperature, the components are not included in the solvent but are included in the total solid content.

[0067] The “weight average molecular weight” refers to a polystyrene-equivalent weight average molecular weight (Mw) based on GPC (gel permeation chromatography).

[0068] Unless otherwise specified, the "amine value" means the amine value converted into effective solid content, and is a value expressed as the mass of KOH equivalent to the amount of alkali per 1g of solid content of the dispersant.

[0069] In addition, the measuring method will be described later.

[0070] Unless otherwise specified, the "acid value" means the acid value converted into effective solid content, and is calculated by neutralization titration.

[0071] With respect to pigments, "CI" means Color Index.

[0072] In this specification, the percentage and part expressed by "mass" have the same meaning as the percentage and part expressed by "weight".

[0073] [Photosensitive coloring resin composition]

[0074] The photosensitive colored resin composition of the present invention contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated compound. Each component will be described in detail.

[0075] <(A) Colorant>

[0076] The photosensitive colored resin composition of the present invention contains (A) a colorant. By containing the (A) colorant, appropriate light absorption can be obtained, and in particular, when used for forming a light shielding member such as a partition wall, appropriate light shielding property can be obtained.

[0077] The type of the colorant (A) that can be used in the photosensitive colored resin composition of the present invention is not particularly limited, and a pigment or a dye may be used. Among them, a pigment is preferably used from the viewpoint of durability.

[0078] The pigment contained in the (A) colorant may be a single type or two or more types. In particular, two or more types are preferably used from the viewpoint of achieving uniform light shielding in the visible region and an optical density per 1 μm film thickness (hereinafter also referred to as “OD per unit film thickness” or “unit OD”) of the coating film obtained by curing the photosensitive coloring composition.

[0079] The type of pigment that can be used as the colorant (A) is not particularly limited, and examples thereof include organic coloring pigments and black pigments. Here, the organic coloring pigment refers to an organic pigment that exhibits a color other than black, and examples thereof include red pigments, orange pigments, blue pigments, violet pigments, green pigments, and yellow pigments.

[0080] Among pigments, from the viewpoint of high resistance and low dielectric constant, organic pigments are preferred. Wherein, from the viewpoint of suppressing the absorption of ultraviolet rays, high curability, and easily controlling the shape of the cured product, organic coloring pigments are preferably used. In addition, from the viewpoint of light-shielding property, organic black pigments are preferably used.

[0081] The organic coloring pigment may be used alone or in combination of two or more. In particular, it is more preferred to use organic coloring pigments of different colors in combination, and it is further preferred to use a combination of organic coloring pigments that exhibit a color close to black.

[0082] The chemical structure of these organic coloring pigments is not particularly limited, and for example, azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene can be cited. Hereinafter, specific examples of usable pigments are represented by pigment numbers. "CI" in the "CI Pigment Red 2" etc. cited below refers to a color index.

[0083] Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149 , 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. From the viewpoint of light blocking property and dispersibility, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 are preferred, and CI Pigment Red 177, 209, 224, 254 are more preferred. CI Pigment Red 177, 254, and 272 are preferred from the viewpoint of dispersibility and light-shielding properties. When the photosensitive coloring resin composition is cured by ultraviolet rays, a red pigment having a low ultraviolet absorption rate is preferred. From this viewpoint, CI Pigment Red 254 and 272 are more preferred.

[0084] Examples of orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. From the viewpoint of dispersibility and light-shielding properties, CI Pigment Orange 13, 43, 64, and 72 are preferably used. When the photosensitive color resin composition is cured by ultraviolet rays, as the orange pigment, a pigment having a low ultraviolet absorption rate is preferred. From this viewpoint, CI Pigment Orange 64 and 72 are more preferred.

[0085] Examples of the blue pigment include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. From the viewpoint of light-shielding properties, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferably used, and CI Pigment Blue 15:6 is more preferably used. CI Pigment Blue 15:6, 16, and 60 are preferred from the viewpoint of dispersibility and light-shielding properties. When the photosensitive color resin composition is cured by ultraviolet rays, a blue pigment having a low ultraviolet absorption rate is preferred. From this viewpoint, CI Pigment Blue 60 is more preferred.

[0086] Examples of the violet pigment 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, CI Pigment Violet 19, 23, and 29 are preferred, and CI Pigment Violet 23 is more preferred. From the viewpoint of dispersibility and light-shielding properties, CI Pigment Violet 23 and CI Pigment Violet 29 are preferred. When the photosensitive coloring resin composition is cured by ultraviolet rays, the violet pigment is preferably a pigment having a low ultraviolet absorptivity. From the viewpoint of the above, CI Pigment Violet 29 is more preferably used.

[0087] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and 59, and CI Pigment Green 7 and 36 are preferred.

[0088] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 8 1, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 1 54, 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, 192, 193, 194, 195, 196. 3, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, preferably CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably CI Pigment Yellow 83, 138, 139, 150, 180.

[0089] From the viewpoint of light-shielding properties and shape control of the cured product, it is preferred to use at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment, and a violet pigment.

[0090] From the viewpoint of light-shielding properties and shape control of the cured product, it is preferred that at least one of the following pigments be contained.

[0091] Red pigment: CI Pigment Red 177, 254, 272

[0092] Orange pigment: CI Pigment Orange 43, 64, 72

[0093] Blue pigment: CI Pigment Blue 15:6, 60

[0094] Violet Pigment: CI Pigment Violet 23, 29

[0095] The combination of organic coloring pigments when two or more organic coloring pigments are used in combination is not particularly limited, but from the viewpoint of light-shielding properties, it is preferred that at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and violet pigments be contained.

[0096] The combination of colors is not particularly limited, and from the viewpoint of light-shielding properties, examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a violet pigment.

[0097] Examples of the black pigment include organic black pigments and inorganic black pigments, among which organic black pigments are preferably used from the viewpoint of light-shielding properties and insulating properties.

[0098] Examples of the organic black pigment include perylene-based black pigments, aniline-based black pigments, and benzodifuranone-based black pigments.

[0099] Examples of the perylene-based black pigment include Lumogen Black (registered trademark) FK4281 and K0087, and Paliogen Black (registered trademark) EH0788 (all manufactured by BASF).

[0100] Examples of the aniline black pigment include Paliotol Black (registered trademark) L0080, D0080, and K0080 (all manufactured by BASF).

[0101] Among organic black pigments, benzodifuranone-based organic black pigments are preferred from the viewpoints of light-shielding properties, dispersibility, developability, and light-emitting properties.

[0102] Among benzodifuranone-based organic black pigments, from the viewpoints of light-shielding properties, dispersibility, developability, and luminescent properties, it is preferred that the organic black pigment comprises at least one selected from the group consisting of a compound represented by the following general formula (A-1-1) (hereinafter sometimes referred to as “compound (A-1-1)”), a geometric isomer of the compound (A-1-1), a salt of the compound (A-1-1), and a salt of a geometric isomer of the compound (A-1-1) (hereinafter sometimes referred to as “organic black pigment represented by formula (A-1-1)”).

[0103] [Chemistry 2]

[0104]

[0105] In formula (A-1-1), R 611 and R 616 Each independently represents a hydrogen atom, CH 3 CF 3 , fluorine atom or chlorine atom; R 612 , R 613 , R 614 , R 615 , R 617 , R 618 , R619 and R 620 Each independently represents a hydrogen atom, a halogen atom, R 621 、COOH、COOR 621 、COO - ,CONH 2 ,CONHR 621 ,CONR 621 R 622 、CN、OH、OR 621 、COCR 621 、OOCNH 2 ,OOCNHR 621 、OOCNR 621 R 622 、NO 2 NH 2 、NHR 621 NR 621 R 622 、NHCOR 622 NR 621 COR 622 、N=CH 2 、N=CHR 621 、N=CR 621 R 622 , SH, SR 621 , SOR 621 、SO 2 R 621 、SO 3 R 621 、SO 3 H.SO 3 - 、SO 2 NH 2 、SO 2 NHR 621 or SO 2 NR 621 R 622 ; Select from R 612 With R 613 , R 613 With R 614 , R 614 With R 615 , R 617 With R 618 , R 618 With R 619 , and R 619 With R 620 At least one of the groups may be directly bonded to each other, or bonded to each other through an oxygen atom, a sulfur atom, NH or NR 621 The bridges are bonded to each other; R 621 and R 622Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

[0106] Compound (A-1-1) and the geometrical isomers of compound (A-1-1) have the following core structure (wherein the substituents in the structural formula are omitted), and the trans-trans isomer is likely to be the most stable.

[0107] [Chemistry 3]

[0108]

[0109] When compound (A-1-1) or a geometric isomer of compound (A-1-1) is anionic, it is preferably a salt whose charge is compensated by any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organic metal complex.

[0110] The substituents of formula (A-1-1) tend to increase the shielding rate, and therefore the following substituents are preferred. This is because the following substituents are considered to have no absorption and do not affect the hue of the pigment.

[0111] R 612 , R 614 , R 615 , R 617 , R 619 and R 620 Each independently is preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.

[0112] R 613 and R 618 are each independently preferably a hydrogen atom, NO 2 、OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 、N(CH 3 ) 2 、N(CH 3 )(C 2 H 5 )、N(C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 - , more preferably a hydrogen atom or SO3 H is particularly preferably a hydrogen atom.

[0113] R 611 and R 616 are each independently preferably a hydrogen atom, CH 3 or CF 3 , and more preferably a hydrogen atom.

[0114] Preferably selected from R 611 and R 616 , R 612 and R 617 , R 613 and R 618 , R 614 and R 619 , and R 615 and R 620 At least one combination of the groups is the same, preferably R 611 With R 616 Same, R 612 With R 617 Same, R 613 With R 618 Same, R 614 With R 619 The same, and R 615 With R 620 same.

[0115] The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.

[0116] Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujayl, norbornyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, adamantane-1-yl and adamantane-2-yl.

[0117] The alkenyl group having 2 to 12 carbon atoms is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

[0118] Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthene-8-yl, 4(10)-thuja-10-yl, 2-norbornene-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcarbadien-3-yl, and camphenyl.

[0119] The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

[0120] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0121] The organic black pigment represented by formula (A-1-1) is preferably an organic black pigment comprising at least one selected from the group consisting of a compound represented by the following general formula (A-1-2) (hereinafter also referred to as "compound (A-1-2)") and geometric isomers of compound (A-1-2).

[0122] [Chemistry 4]

[0123]

[0124] As compound (A-1-2), trade name Irgaphor (registered trademark) Black S 0100CF (manufactured by BASF) can be mentioned, for example.

[0125] The organic black pigment is preferably dispersed by a dispersant, solvent, or method described below. In addition, if a sulfonic acid derivative of compound (A-1-1), particularly a sulfonic acid derivative of compound (A-1-2), is present during dispersion, dispersibility and storage properties may be improved, so the organic black pigment preferably contains these sulfonic acid derivatives.

[0126] On the other hand, as the inorganic pigment, it is preferred to use an inorganic black pigment from the viewpoint of higher light-shielding properties.

[0127] Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.

[0128] From the viewpoint of light-shielding property and image characteristics, carbon black can be preferably used. Examples of carbon black include the following.

[0129] Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #9 60, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #315 0, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B.

[0130] Made by Degussa: Printex (registered trademark, the same below.) 3. Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, PrintexV, Special Black 550, Special Black 350, Special Black 250, Special Black100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color BlackFW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170.

[0131] Made by Cabot Corporation: Monarch (registered trademark, the same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, the same below) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 550R, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark) -8.

[0132] Made by Birla: RAVEN (registered trademark, the same below.) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN10 00, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

[0133] Carbon black whose surface has been subjected to an acid treatment can be used. For example, the carbon black described in Japanese Patent Gazette No. 3674086 can be preferably used. In addition, carbon black coated with resin can be used. When using carbon black coated with resin, it has the effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black coated with resin, for example, the carbon black described in Japanese Patent Gazette No. 09-71733 can be preferably used. In terms of volume resistance and dielectric constant, resin-coated carbon black is preferably used.

[0134] The pigment is preferably dispersed and used so that the average particle size is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.25 μm or less. Here, the basis of the average particle size is the number of pigment particles.

[0135] The average particle size of the pigment is obtained from the pigment particle size measured by dynamic light scattering (DLS). The particle size is measured at 25°C for a sufficiently diluted photosensitive coloring resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring equipment, it is used).

[0136] In addition to the pigment, a dye may be used as the (A) colorant.

[0137] Examples of dyes that can be used as the colorant (A) include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0138] Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0139] Examples of the anthraquinone dye include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0140] As a phthalocyanine dye, CI Vat Blue 5 is mentioned, for example.

[0141] Examples of the quinoneimine dye include CI Basic Blue 3 and CI Basic Blue 9.

[0142] Examples of the quinoline dye include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64.

[0143] Examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0144] <(B) Dispersant>

[0145] The photosensitive color resin composition of the present invention contains a dispersant (B) for the purpose of ensuring the stability of quality, finely dispersing the colorant (A) and stabilizing the dispersion state thereof.

[0146] As the (B) dispersant, a polymer dispersant having a functional group is preferred, and further, from the viewpoint of dispersion stability, a polymer dispersant having the following functional groups is more preferred: a carboxyl group, a phosphoric acid group, a sulfonic acid group, or a base thereof; a primary amino group, a secondary amino group, or a tertiary amino group; a quaternary ammonium group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine. From the viewpoint of being able to disperse the pigment with a small amount of dispersant, a polymer dispersant having a basic functional group such as a primary amino group, a secondary amino group, or a tertiary amino group; a quaternary ammonium group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine is further preferred.

[0147] Examples of the polymer dispersant include carbamate dispersants, acrylic acid dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants containing monomers having an amino group and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0148] Examples of such dispersants include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK), DISPARLON (registered trademark, manufactured by Kusumoto Chemicals), SOLSPERSE (registered trademark, manufactured by The Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0149] The polymer dispersants may be used alone or in combination of two or more.

[0150] From the viewpoint of the dispersibility of the pigment, the (B) dispersant preferably contains either or both of a urethane polymer dispersant and an acrylic polymer dispersant having a functional group, and particularly preferably contains an acrylic polymer dispersant.

[0151] From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having either or both of a polyester bond and / or a polyether bond is preferred.

[0152] Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, and BYK-LPN21116 (all acrylic-based) (all manufactured by BYK-Chemie).

[0153] The amine value of the polymer dispersant having a basic functional group is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. In addition, it is preferably 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, further preferably 100 mgKOH / g or less, further preferably 90 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 140 mgKOH / g, more preferably 10 to 120 mgKOH / g, further preferably 20 to 100 mgKOH / g, further preferably 40 to 90 mgKOH / g, and particularly preferably 50 to 80 mgKOH / g. By setting it to above the above lower limit, there is a tendency for the dispersibility to become good. By setting it to the said upper limit value or less, there exists a tendency for the compatibility with (C) alkali-soluble resin to become favorable.

[0154] From the viewpoint of dispersibility, the acrylic dispersant is preferably an AB or BAB block copolymer composed of an A block having the above-mentioned functional group and a B block not having the above-mentioned functional group. In this case, in the A block, in addition to the partial structure derived from the unsaturated group-containing monomer containing the above-mentioned functional group, a partial structure derived from the unsaturated group-containing monomer not containing the above-mentioned functional group may also be contained, and they may be contained in the A block in any manner of random copolymerization or block copolymerization. The content ratio of the partial structure not containing a functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, further preferably 10% by mass or less, and particularly preferably 0% by mass.

[0155] From the viewpoint of dispersibility, the B block is preferably composed only of a partial structure derived from an unsaturated group-containing monomer that does not contain the above-mentioned functional group. One B block may contain partial structures derived from two or more monomers, which may be contained in the B block in either a random copolymer or a block copolymer.

[0156] The AB or BAB block copolymer can be prepared, for example, by the living polymerization method shown below.

[0157] Living polymerization methods include anionic living polymerization, cationic living polymerization, and radical living polymerization. Among them, in anionic living polymerization, the polymerization active species is an anion, which is represented by the following scheme, for example.

[0158] [Chemistry 5]

[0159]

[0160] In the above scheme, Ar 1 It is a monovalent organic group, Ar 2 For Ar 1 In different monovalent organic groups, M is a metal atom, and s and t are each an integer greater than 1.

[0161] In the radical living polymerization method, the polymerization active species is a radical, which is represented by the following scheme, for example.

[0162] [Chemistry 6]

[0163]

[0164] In the above scheme, Ar 1 It is a monovalent organic group, Ar 2 For Ar 1 different monovalent organic groups, j and k are each an integer greater than 1, R a is a hydrogen atom or a monovalent organic group, R b For R a Different hydrogen atoms or monovalent organic groups.

[0165] When synthesizing an acrylic dispersant, for example, the following can be used: Japanese Patent Application Laid-Open No. 9-62002, P. Lutz, P. Masson, et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews, et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985), K. Hatada, K. Ute, et al., Polym. J. 18, 1037 (1986), Koichi Yuhei, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collected Works of Polymers, 46, 18 9 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al., Macromolecules, 20, 1473 (1987), Japanese Patent Publication No. 2013-119568, Japanese Patent Publication No. 2017-182092, Japanese Patent Publication No. 2017-019937, International Publication No. 2019 / 107020, International Publication No. 2008 / 156148, and Japanese Patent Publication No. 2010-256509.

[0166] The acrylic dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block / B block ratio constituting the copolymer is not particularly limited, but is preferably 1 / 99 to 80 / 20 (mass ratio), and more preferably 5 / 95 to 60 / 40 (mass ratio). By setting it within this range, there is a tendency to easily ensure a balance between dispersibility and storage stability.

[0167] The amount of the quaternary ammonium group in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By setting the amount within this range, it tends to be easy to ensure good dispersibility.

[0168] Such acrylic dispersants may contain amino groups. The amine value of the acrylic dispersant is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. In addition, it is preferably 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, further preferably 100 mgKOH / g or less, further preferably 90 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, preferably 1 to 140 mgKOH / g, more preferably 10 to 120 mgKOH / g, further preferably 20 to 100 mgKOH / g, further preferably 40 to 90 mgKOH / g, and particularly preferably 50 to 80 mgKOH / g. By setting it to above the above lower limit, there is a tendency for the dispersibility to become good. By setting it to the said upper limit value or less, there exists a tendency for the compatibility with (C) alkali-soluble resin to become favorable.

[0169] The amine value of the acrylic dispersant is expressed as the mass of KOH equivalent to the amount of alkali per 1 g of the solid content excluding the solvent in the dispersant sample, and is measured by the following method.

[0170] 0.5-1.5 g of the dispersant sample was accurately weighed in a 100 mL beaker and dissolved in 50 mL of acetic acid. The solution was titrated with 0.1 mol / L HClO using an automatic titrator equipped with a pH electrode. 4 The acetic acid solution was subjected to neutralization titration. The inflection point of the titration pH curve was taken as the titration end point, and the amine value was calculated by the following formula.

[0171] Amine value [mgKOH / g] = (561×V) / (W×S)

[0172] [W represents the amount of the dispersant sample weighed [g], V represents the titration amount at the titration endpoint [mL], and S represents the solid content concentration of the dispersant sample [mass %].]

[0173] The weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is preferably 50000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1000 to 50000, more preferably 3000 to 50000, further preferably 4000 to 20000, and particularly preferably 5000 to 15000. By setting it to above the aforementioned lower limit, there is a tendency for dispersibility to become good, and by setting it to below the aforementioned upper limit, there is a tendency that viscosity changes are not easily caused.

[0174] The acrylic dispersant preferably has a tertiary amino group and / or a quaternary ammonium group.

[0175] When the acrylic dispersant has a quaternary ammonium group as a functional group, the chemical structure of the repeating unit containing the quaternary ammonium group is not particularly limited. From the viewpoint of dispersibility, the acrylic dispersant preferably has a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as "repeating unit (V)").

[0176] [Chemistry 7]

[0177]

[0178] In formula (V), R 31 ~R 33 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R 31 ~R 33 Two or more of R may be bonded to each other to form a ring structure. 34 is a hydrogen atom or a methyl group. X is a divalent linking group, Y - as counter anion.

[0179] R of formula (V) 31 ~R 33 The alkyl group which may have a substituent may be any of a straight chain or a branched chain. In addition, a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group may also be included. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, and is preferably 10 or less, more preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. For example, 1 to 10 are preferred, 1 to 6 are more preferred, 1 to 4 are further preferred, and 1 to 2 are particularly preferred.

[0180] Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, preferably methyl, ethyl, propyl, butyl, pentyl and hexyl groups, more preferably methyl, ethyl, propyl and butyl groups, further preferably methyl and ethyl groups.

[0181] R of formula (V) 31 ~R 33 The number of carbon atoms of the aryl group which may have a substituent is not particularly limited, but is preferably 6 or more, and preferably 16 or less, and more preferably 12 or less. For example, it is preferably 6 to 16, and more preferably 6 to 12. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl, and phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl are preferred, and phenyl, methylphenyl, and ethylphenyl are more preferred.

[0182] R of formula (V)31 ~R 33 The number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is preferably 7 or more, preferably 16 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. For example, 7 to 16 are preferred, 7 to 12 are more preferred, 7 to 10 are further preferred, and 7 to 8 are particularly preferred. Examples of the aralkyl group include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl, preferably phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl, and more preferably phenylmethyl and phenylethyl.

[0183] From the viewpoint of dispersibility, R 31 ~R 33 Each independently is an alkyl or aralkyl group, preferably R 31 ~R 33 Each is independently methyl or phenylmethyl.

[0184] As Y in formula (V) - For example, Cl - Br - ,I - , ClO 4 - , BF 4 - , CH 3 COO - PF - , CH 3 SO 4 - , C 2 H 5 SO 4 - From the viewpoint of dispersibility, it is preferred that halogen is contained, and from the viewpoint of driving voltage in an organic electroluminescent element, it is preferred that halogen is not contained. More preferably, CH 3 SO 4 - , C 2 H 5 SO 4 - .

[0185] In addition, aromatic dicarboxylic acid imide anions, aromatic sulfonate anions, aromatic phosphonate anions, and aromatic carboxylate anions described in International Publication No. 2018 / 079659; and alkyl sulfate anions and alkyl sulfonate anions described in International Publication No. 2019 / 107020 can also be preferably used.

[0186] As Y - From the perspective of the development form, Cl is preferred. -From the viewpoint of light emitting properties, alkylsulfonate anions are preferred.

[0187] When the polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following general formula (VI) (hereinafter sometimes referred to as "repeating unit (VI)") from the viewpoint of dispersibility and light emitting properties.

[0188] [Chemistry 8]

[0189]

[0190] In formula (VI), R 35 and R 36 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R 35 and R 36 Can bond with each other to form a ring structure. 37 is a hydrogen atom or a methyl group. Z is a divalent linking group.

[0191] As R of formula (VI) 35 and R 36 The alkyl group which may have a substituent may preferably be used as R of formula (V): 31 ~R 33 The alkyl groups exemplified are:

[0192] As R of formula (VI) 35 and R 36 The aryl group which may have a substituent may preferably be used as R of formula (V): 31 ~R 33 The aryl groups exemplified are:

[0193] As R of formula (VI) 35 and R 36 The aralkyl group which may have a substituent may preferably be R 31 ~R 33 The aralkyl groups exemplified are:

[0194] From the perspective of dispersibility and luminescence properties, R 35 and R 36 Each independently is preferably an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

[0195] As R of formula (V) 31 ~R 33 and R of formula (VI) 35 and R 36 The substituent that the alkyl group, aralkyl group or aryl group in the group may have includes, for example, a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

[0196] Examples of X in formula (V) and Z in formula (VI) include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 -base, -COOR 44 -base (where R 43 and R 44 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms, preferably -COO-R 44 - group, more preferably -COO-C 2 H 4 -base.

[0197] From the viewpoint of dispersibility, it is preferred to have a repeating unit (V), and further from the viewpoint of light-emitting properties, it is preferred to have a repeating unit (V) and a repeating unit (VI).

[0198] The proportion of the repeating unit (V) in all the repeating units of the dispersant is not particularly limited. From the perspective of dispersibility, it is preferably 1 mol% or more, more preferably 3 mol% or more, further preferably 5 mol% or more, and particularly preferably 8 mol% or more. In addition, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 1 to 50 mol%, 3 to 30 mol%, 5 to 20 mol%, or 8 to 15 mol%.

[0199] The proportion of the repeating unit (VI) in all the repeating units of the dispersant is not particularly limited. From the perspective of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, and particularly preferably 20 mol% or more. In addition, it is preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 5 to 60 mol%, 10 to 40 mol%, 15 to 30 mol%, or 20 to 25 mol%.

[0200] From the viewpoint of improving the compatibility of the solvent and the like with the alkali-soluble resin component and improving dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following general formula (VII) (hereinafter sometimes referred to as "repeating unit (VII)").

[0201] [Chemistry 9]

[0202]

[0203] In formula (VII), R 40 is ethylene or propylene, R 41 is an alkyl group which may have a substituent, R 42 is a hydrogen atom or a methyl group. n is an integer of 1 to 20.

[0204] R of formula (VII) 41 The alkyl group which may have a substituent may be any of a straight chain or a branched chain. In addition, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may also be included. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, and more preferably methyl, ethyl, propyl, and butyl groups.

[0205] From the viewpoint of compatibility and dispersibility of the solvent etc. with the alkali-soluble resin component, n in formula (VII) is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1 to 10, more preferably 2 to 5.

[0206] The proportion of the repeating unit (VII) in all the repeating units of the dispersant is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 4 mol% or more. In addition, it is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 1 to 30 mol%, 2 to 20 mol%, or 4 to 10 mol%. In the case of the aforementioned range, there is a tendency to easily take into account the compatibility and dispersion stability of the solvent and the like to the alkali-soluble resin component.

[0207] From the viewpoint of improving the compatibility of the dispersant solvent and the like with the alkali-soluble resin component and improving dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following general formula (VIII) (hereinafter sometimes referred to as "repeating unit (VIII)").

[0208] [Chemistry 10]

[0209]

[0210] In formula (VIII), R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. 39 A hydrogen atom or a methyl group.

[0211] R of formula (VIII)38 The alkyl group which may have a substituent may be any of a straight chain or a branched chain. In addition, a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group may also be included. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more. In addition, it is preferably 10 or less, and more preferably 8 or less. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, and 2-ethylhexyl, and more preferably methyl, ethyl, propyl, butyl, and 2-ethylhexyl.

[0212] R of formula (VIII) 38 The number of carbon atoms of the aryl group which may have a substituent is not particularly limited, but is preferably 6 or more. In addition, it is preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. For example, it is preferably 6 to 16, more preferably 6 to 12, and further preferably 6 to 8. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl, preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl, and more preferably phenyl, methylphenyl, and ethylphenyl.

[0213] R of formula (VIII) 38 The number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is preferably 7 or more, and preferably 16 or less, more preferably 12 or less, and further preferably 10 or less. For example, 7 to 16 are preferred, 7 to 12 are more preferred, and further preferably 7 to 10 are preferred. Examples of the aralkyl group include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl, and phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl are preferred, and phenylmethyl and phenylethyl are more preferred.

[0214] From the viewpoint of solvent compatibility and dispersion stability, R 38 Preferred is an alkyl group or an aralkyl group, and more preferred is a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group, or a phenylmethyl group.

[0215] As R 38 The substituents that the alkyl group in the formula (R) may have include, for example, a halogen atom and an alkoxy group. The substituents that the aryl group or the aralkyl group may have include, for example, a chain alkyl group, a halogen atom and an alkoxy group. 38 The chain alkyl group represented includes both linear and branched ones.

[0216] From the viewpoint of dispersibility, the content ratio of repeating unit (VIII) in all repeating units of the dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 50 mol% or more. In addition, it is preferably 80 mol% or less, more preferably 70 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 30 to 80 mol%, 40 to 80 mol%, or 50 to 70 mol%.

[0217] The acrylic dispersant may have repeating units other than the repeating unit (V), the repeating unit (VI), the repeating unit (VII) and the repeating unit (VIII). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; and monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether and N-methacryloylmorpholine.

[0218] From the viewpoint of further improving dispersibility, the acrylic dispersant is preferably a block copolymer having an A block and a B block, wherein the A block has a repeating unit (V) and a repeating unit (VI), and the B block does not have a repeating unit (V) and a repeating unit (VI). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium group but also a tertiary amino group into the A block, there is unexpectedly a tendency that the dispersing ability of the dispersant is significantly improved. In addition, it is preferred that the B block has a repeating unit (VII), and more preferably further has a repeating unit (VIII).

[0219] In the A block, the repeating unit (V) and the repeating unit (VI) may be contained in the form of random copolymerization or block copolymerization. In addition, two or more repeating units (V) and repeating units (VI) may be contained in one A block, respectively. In this case, each repeating unit may be contained in the A block in the form of random copolymerization or block copolymerization.

[0220] Repeating units other than repeating units (V) and repeating units (VI) may also be contained in the A block, and examples of such repeating units include repeating units derived from the aforementioned (meth)acrylate monomers. The content of repeating units other than repeating units (V) and repeating units (VI) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but it is particularly preferred that the A block does not contain such repeating units.

[0221] Repeating units other than repeating units (VII) and repeating units (VIII) may also be contained in the B block. Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as N-methylolacrylamide; and monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloylmorpholine. The content of repeating units other than repeating units (VII) and repeating units (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but it is particularly preferred that the repeating units are not contained in the B block.

[0222] These acrylic dispersants may be used alone or in combination of two or more.

[0223] <(C) Alkali-soluble resin>

[0224] The alkali-soluble resin (C) in the present invention contains a polyamideimide (meth)acrylate resin (C-1) (hereinafter sometimes referred to as "alkali-soluble resin (C-1)") obtained by the reaction of a polyamideimide resin having a terminal acid group or anhydride group, a (meth)acrylate having an epoxy group in the molecule, and a (di)tricarboxylic anhydride. The polyamideimide resin is obtained by the reaction of an isocyanurate-type polyisocyanate and tricarboxylic anhydride.

[0225] Here, (di)tricarboxylic acid anhydride means dicarboxylic acid anhydride and / or tricarboxylic acid anhydride.

[0226] Polyamideimide (meth) acrylate resin (C-1) can also be expressed as a resin obtained by reacting compound (C-1-2), compound (C-1-3) and polyamideimide resin (C-1-1). It should be noted that polyamideimide (meth) acrylate resin (C-1) also includes a resin obtained by reacting polyamideimide resin (C-1-1), compound (C-1-2) and compound (C-1-3). Here, polyamideimide resin (C-1-1) is a polyamideimide resin having a terminal acid group or anhydride group obtained by reacting compound (C-1-11) with compound (C-1-12).

[0227] In addition, the compound (C-1-11) represents an isocyanurate type polyisocyanate.

[0228] In addition, compound (C-1-12) represents a tricarboxylic acid anhydride.

[0229] In addition, the compound (C-1-2) represents a (meth)acrylate having an epoxy group in the molecule.

[0230] In addition, the compound (C-1-3) represents a dicarboxylic anhydride and / or a tricarboxylic anhydride.

[0231] <Alkali-soluble resin (C-1)>

[0232] The alkali-soluble resin (C-1) has an isocyanurate skeleton, an amide bond, and an imide bond, so that the intermolecular force is strong and it tends to be difficult to thermally decompose during heat treatment. It is believed that by containing the alkali-soluble resin (C-1) in the photosensitive color resin composition, the generation of smoke when the cured film of the composition is fired is small. In addition, it is believed that the alkali-soluble resin (C-1) has a (meth)acryloyl group, so that even if a colorant is contained, it can be cured by light or heat to form a more solid cured film, and the residual film rate after firing can be improved.

[0233] Examples of the compound (C-1-11), i.e., the isocyanurate type polyisocyanate, include, for example, isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from hexamethylene diisocyanate, isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from trimethylhexamethylene diisocyanate, isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from isophorone diisocyanate, isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from toluene diisocyanate, isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated toluene diisocyanate, and isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated toluene diisocyanate. The invention relates to isocyanurate-type triisocyanates (including polymers such as pentamers) synthesized from xylene diisocyanate, isocyanurate-type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated xylene diisocyanate, isocyanurate-type triisocyanates (including polymers such as pentamers) synthesized from norbornane diisocyanate, isocyanurate-type triisocyanates (including polymers such as pentamers) synthesized from diphenylmethane diisocyanate, and isocyanurate-type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated diphenylmethane diisocyanate.

[0234] From the viewpoint of suppressing smoke, alicyclic isocyanurate type polyisocyanates are preferred, and isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from isophorone diisocyanate, isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated toluene diisocyanate, and isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated xylene diisocyanate are more preferred, and isocyanurate type triisocyanates (including polymers such as pentamers) synthesized from isophorone diisocyanate are further preferred.

[0235] Examples of the compound (C-1-12), that is, tricarboxylic anhydride, include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic anhydride, propanetricarboxylic anhydride, cyclohexanetricarboxylic anhydride, methylcyclohexanetricarboxylic anhydride, cyclohexenetricarboxylic anhydride, and methylcyclohexenetricarboxylic anhydride.

[0236] Examples of cyclohexanetricarboxylic anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, and cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride.

[0237] From the viewpoint of suppressing smoke, alicyclic tricarboxylic acid anhydrides are preferred, and cyclohexanetricarboxylic acid is preferred.

[0238] The compound (C-1-2), that is, the (meth)acrylate having an epoxy group in the molecule, has no particular limitation on other structures as long as it has an epoxy group and a (meth)acryloyl group in the molecular structure.

[0239] Examples of (meth)acrylates having an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, cyclohexyl monoepoxy acrylate, or derivatives thereof (e.g., analogs obtained by reacting acrylic acid or methacrylic acid with an epoxycyclohexane compound, such as 3,4-epoxycyclohexylmethyl methacrylate). These may be used alone or in combination of two or more. From the perspective of a polyamide-imide resin containing an ethylenically unsaturated group, an acid group, and a secondary hydroxyl group having excellent heat resistance as a cured product, a compound having a molecular weight of 1,000 or less is preferred.

[0240] As the tricarboxylic anhydride in the compound (C-1-3), the same compound as the compound (C-1-12) can be used.

[0241] Examples of the dicarboxylic anhydride in the compound (C-1-3) include anhydrides of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, and methyltetrahydrophthalic acid.

[0242] From the viewpoint of suppressing smoke, alicyclic tricarboxylic acid anhydrides are preferred, anhydrides of hexahydrophthalic acid and methylhexahydrophthalic acid are more preferred, and anhydride of hexahydrophthalic acid is further preferred.

[0243] The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (C-1) measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, further preferably 2500 or more, and further preferably 3000 or more. In addition, it is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10000 or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 2000 to 10000, and further preferably 3000 to 10000. By setting it to above the aforementioned lower limit, there is a tendency to reduce the generation of smoke. By setting it to below the aforementioned upper limit, there is a tendency for the developing solubility to become good.

[0244] The acid value of the alkali-soluble resin (C-1) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, and further preferably 60 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 20 to 200 mgKOH / g, more preferably 40 to 200 mgKOH / g, and further preferably 60 to 150 mgKOH / g.

[0245] When the content is equal to or more than the above lower limit, the developing solubility tends to be improved and the resolution tends to be good. When the content is equal to or less than the above upper limit, the residual film rate tends to be good.

[0246] The alkali-soluble resin (C-1) can be prepared using a known method, such as the method described in Japanese Patent Application Laid-Open Nos. 2023-55304, 2023-55622, and 2023-55623.

[0247] The polyamideimide (meth)acrylate resin (C-1) in the present invention is produced through two reaction steps.

[0248] First, there is a step of reacting an isocyanurate type polyisocyanate (C-1-11) with a tricarboxylic anhydride (C-1-12) to obtain a polyamideimide resin (C-1-1) (referred to as an "amide imidization step").

[0249] Next, there is a step (referred to as "carboxylation step") of reacting the obtained polyamideimide resin (C-1-1), a (meth)acrylate compound (C-1-2) having an epoxy group in the molecule, and dicarboxylic anhydride and / or tricarboxylic anhydride (C-1-3).

[0250] First, the amide imidization step will be described in detail.

[0251] The isocyanurate type polyisocyanate (C-1-11) used for producing the polyamide-imide resin (C-1-1) in the present invention is obtained by isocyanurating a diisocyanate compound in the presence or absence of a trimerization catalyst.

[0252] The trimerization catalyst is not particularly specified, but examples thereof include amine compounds such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-s-triazine, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms such as potassium acetate, potassium 2-ethylhexanoate, and potassium octoate, and quaternary ammonium salts of carboxylic acids. Examples of commercially available products include DABCOP15 (manufactured by Sankyo Air Products), DABCOK15 (manufactured by Sankyo Air Products), PELCAT9540 (manufactured by PELRON), DABCOTMR (manufactured by Sankyo Air Products), TOYOCATTR20 (manufactured by Tosoh), and U-CAT18X (manufactured by San-Apro).

[0253] In the reaction of isocyanurate polyisocyanate (C-1-11) and tricarboxylic anhydride (C-1-12), the total amount of anhydride group and carboxylic acid is preferably 1.0 mol to 3.0 mol, more preferably 1.2 mol to 2.8 mol, and further preferably 1.4 mol to 2.6 mol, relative to 1 mol of isocyanate group possessed by isocyanurate polyisocyanate (C-1-11). When the total amount of anhydride group and carboxylic acid exceeds 1.0 mol, the residue of isocyanate group is prevented, the high molecular weight is suppressed, and the developability becomes good. If the total amount of anhydride group and carboxylic acid is less than 3.0 mol, there is a tendency that smoke is suppressed.

[0254] The amide imidization step is solvent-free or uses an organic solvent without hydroxyl groups. Specifically, the reaction can be carried out in a single or mixed solvent of the following substances:

[0255] Ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and other ethylene glycol dialkyl ethers;

[0256] Polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether;

[0257] Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and other ethylene glycol monoalkyl ether acetates;

[0258] Polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate and triethylene glycol monobutyl ether acetate;

[0259] Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether;

[0260] Polypropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol dibutyl ether;

[0261] Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate;

[0262] Polypropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate and tripropylene glycol monobutyl ether acetate;

[0263] or dialkyl ethers of copolyether glycols such as low molecular weight ethylene-propylene copolymers, monoacetate monoalkyl ethers of copolyether glycols; or

[0264] Alkyl esters of these polyether diols.

[0265] The amide imidization reaction is preferably carried out by mixing one or more isocyanurate polyisocyanates (C-1-11) and one or more tricarboxylic anhydrides (C-1-12) in a solvent or without a solvent and heating the mixture while stirring.

[0266] The reaction temperature of the amide imidization reaction is preferably in the range of 50°C to 250°C, and particularly preferably in the range of 70°C to 180°C. By setting the reaction temperature to this, the reaction rate becomes faster. During the reaction, along with decarbonation, the anhydride group and the isocyanate group form an imide group, and the carboxylic acid group and the isocyanate group form an amide group. During the reaction, an antioxidant, a leveling agent, a defoaming agent, a surfactant, etc. may be used as needed.

[0267] The amide imidization reaction can be carried out by infrared spectroscopy, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, 1 H-NMR, 13 C-NMR, quantitative analysis of isocyanate groups, etc.

[0268] In infrared spectroscopy, 2270 cm-1 is the characteristic absorption wavelength of isocyanate group. -1 As the reaction decreases, further at 1860cm -1 and 850cm-1 The anhydride groups with characteristic absorption decreased. On the other hand, at 1780 cm -1 and 1720cm -1 The reaction was continued until the absorption of the isocyanate group reached 2270 cm -1 It is preferred that the reaction is easily controlled until the ions disappear.

[0269] The preferred molecular weight range of the polyamide-imide resin (C-1-1) is a range of 1000 to 20,000, more preferably 1,500 to 15,000, and particularly preferably 2000 to 10,000, as measured by GPC in terms of polystyrene conversion weight average molecular weight.

[0270] Next, the carboxylic acid esterification step will be described in detail.

[0271] From the viewpoints of cure shrinkage, sensitivity, and smoke, the molar ratio ((C-1-2) / (C-1-12)) of the (meth)acrylate compound (C-1-2) having an epoxy group in the molecule to the tricarboxylic anhydride (C-1-12) is preferably in the range of 0.8 to 2.0, more preferably 0.9 to 1.8, and even more preferably 1.0 to 1.5.

[0272] From the viewpoint of developability and storage stability, the molar ratio ((C-1-3) / (C-1-2)) of the dicarboxylic anhydride and / or tricarboxylic anhydride (C-1-3) to the (meth)acrylate compound (C-1-2) having an epoxy group in the molecule is preferably in the range of 0.05 to 1.5, and more preferably 0.1 to 1.2.

[0273] During the reaction, a thermal polymerization inhibitor is preferably added to inhibit the thermal polymerization reaction. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-tert-butyl-p-cresol.

[0274] During the reaction, a catalyst is preferably used to promote the reaction. Examples of the catalyst include dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylantimony, methyltriphenylantimony, chromium 2-ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethyl sulfide, and diphenyl sulfide.

[0275] The reaction temperature is preferably 60 to 150° C. The reaction time is preferably 3 to 60 hours.

[0276] The carboxylic acid esterification step may be carried out without a solvent or by diluting with an organic solvent. Examples of the organic solvent include the same solvents as exemplified in the amide imidization step.

[0277] The reaction temperature in the carboxylic acid esterification step is preferably 60° C. to 160° C., more preferably 70° C. to 150° C. The reaction time is preferably 3 to 60 hours.

[0278] The reaction in the carboxylation step is preferably carried out until the epoxy equivalent (solid content epoxy equivalent) becomes 10,000 g / eq or more. The solid content epoxy equivalent is measured by a conventional neutralization titration method in accordance with JIS K 7236. In addition, if the resin concentration in the solution is known, the solid content epoxy equivalent can also be calculated from the epoxy equivalent of the solution and obtained.

[0279] (C) The alkali-soluble resin in the photosensitive coloring resin composition used in the present invention contains an alkali-soluble resin other than the polyamideimide (meth)acrylate resin (C-1).

[0280] As alkali-soluble resins other than polyamideimide (meth)acrylate resin (C-1), there is no particular limitation as long as the resin is alkali-soluble, and examples thereof include resins containing carboxyl groups or hydroxyl groups, and more specifically, examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing polyurethane resins, novolac resins, and polyvinylphenol resins having aromatic rings in the main chain. From the viewpoint of residual film rate and cone angle control, epoxy (meth)acrylate resins (C-2) having aromatic rings in the main chain are preferred (hereinafter sometimes referred to as "epoxy (meth)acrylate resins (C-2)", "alkali-soluble resins (C-2)").

[0281] <Epoxy (meth)acrylate resin having an aromatic ring in the main chain (C-2)>

[0282] The epoxy (meth)acrylate resin (C-2) having an aromatic ring in the main chain is a resin obtained by further reacting a hydroxyl group generated by the reaction of an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion with a compound having two or more substituents capable of reacting with the hydroxyl group, such as a polybasic acid and / or its anhydride.

[0283] The epoxy (meth)acrylate resin (C-2) also includes a resin obtained by reacting a compound having two or more substituents reactive with a hydroxyl group before reacting a polybasic acid and / or anhydride with a hydroxyl group, and then reacting the polybasic acid and / or anhydride with the hydroxyl group.

[0284] Moreover, the resin obtained by making the carboxyl group of the resin obtained by the above reaction further react with a compound having a reactive functional group is also included in the epoxy (meth)acrylate resin (C-2).

[0285] Thus, epoxy (meth)acrylate resins do not substantially have epoxy groups in their chemical structure and are not limited to "(meth)acrylates", but are named as such according to common usage because epoxy compounds (epoxy resins) are raw materials and "(meth)acrylates" are representative examples.

[0286] As the epoxy (meth)acrylate resin (C-2) used in the present invention, from the viewpoint of residual film rate and taper angle control, it is preferred to use the following epoxy (meth)acrylate resin (C2-1) and / or epoxy (meth)acrylate resin (C2-2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin").

[0287] As the epoxy (meth) acrylate resin (C-2), a resin having an aromatic ring in the main chain can be used from the viewpoint of the residual film rate. By containing a large amount of aromatic rings in the main chain, the developer resistance during development in the photosensitive color resin composition is high, and the heat resistance during firing is high, so there is a tendency for the residual film rate to increase.

[0288] <Epoxy (meth)acrylate resin (C2-1)>

[0289] The alkali-soluble resin is obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof.

[0290] <Epoxy (meth)acrylate resin (C2-2)>

[0291] The alkali-soluble resin is obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting the epoxy resin with a polyol and a polybasic acid and / or an anhydride thereof.

[0292] Here, epoxy resin also comprises the raw material compound before forming resin by thermosetting, and as this epoxy resin, can suitably select to use from known epoxy resin.In addition, epoxy resin can use the compound that makes phenolic compound and epihalohydrin react and obtain.As phenolic compound, preferably have the compound of phenolic hydroxyl group more than 2 yuan, can be monomer, also can be polymer.

[0293] As the type of epoxy resin used as a raw material, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, an epoxy resin which is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and an epihalohydrin, an epoxy resin containing an adamantyl group, and a fluorene type epoxy resin can be preferably used. Among them, an epoxy resin having an aromatic ring in the main chain can be more preferably used.

[0294] As the epoxy resin, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, "jER807", "EP-4001" manufactured by Mitsubishi Chemical Corporation) can be preferably used. , "EP-4002", "EP-4004", etc.), epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S type epoxy resins, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, Dow Chemical Co., Ltd.), (o-, m-, p-) cresol novolac type epoxy resins (e.g., "EOCN (registered trademark, hereinafter the same.) -102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), trisphenol methane type epoxy resins (e.g., "EPPN (registered trademark, hereinafter the same.) -501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resins ("CELLOXIDE (registered trademark, hereinafter the same.) 2021P", "CELLOXIDE EHPE" manufactured by Daicel Corporation), epoxy resins obtained by glycidylating a phenolic resin obtained by reacting dicyclopentadiene with phenol (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (C2α) to (C2δ). Specifically, for example, there can be mentioned “XD-1000” manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (C2α), “NC-3000” and “NC-3500” manufactured by Nippon Kayaku Co., Ltd., which are epoxy resins represented by the following general formula (C2β), “E-201” manufactured by Osaka Organic Chemical Industries, Ltd., which is an epoxy resin represented by the following general formula (C2γ), and “ESF-300” manufactured by Nippon Steel & Sumigin Chemical Corporation, which is an epoxy resin represented by the following general formula (C2δ).

[0295] [Chemistry 11]

[0296]

[0297] In formula (C2α), a is an average value, representing a number from 0 to 10, and R 111 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 111 They may be the same or different.

[0298] [Chemistry 12]

[0299]

[0300] In the formula (C2β), b1 and b2 are average values, each independently representing a number from 0 to 10, and R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 121 They may be the same or different.

[0301] [Chemistry 13]

[0302]

[0303] In formula (C2γ), X represents a linking group represented by the following general formula (C2γ-1) or (C2γ-2), wherein the molecular structure contains one or more adamantane structures, and c represents 2 or 3.

[0304] [Chemistry 14]

[0305]

[0306] In formula (C2γ-1) and (C2γ-2), R 131 ~R 134 and R 135 ~R 137 Each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bonding end.

[0307] [Chemistry 15]

[0308]

[0309] In the formula (C2δ), p and q each independently represent an integer of 0 to 4, and R 141 and R 142 Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 143 and R 144 Each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer greater than 0.

[0310] As the epoxy resin, an epoxy resin represented by any one of formulas (C2α) to (C2δ) is preferably used.

[0311] Examples of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth)acrylic acid having an α-halogenated alkyl, alkoxy, halogen, nitro or cyano substituent, and the like; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylsuccinic acid, 2-(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2- (Meth)acryloxypropylphthalic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxybutylsuccinic acid, 2-(meth)acryloxybutyladipic acid, 2-(meth)acryloxybutylhydrophthalic acid, 2-(meth)acryloxybutylphthalic acid, 2-(meth)acryloxybutylmaleic acid, a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid; or a monomer obtained by adding succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride) and the like to hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate; (meth)acrylic acid dimer. In terms of sensitivity, (meth)acrylic acid is preferred.

[0312] As a method for adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150°C. As the esterification catalyst used here, for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

[0313] Each component of the epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be selected and used alone, or two or more components may be used in combination.

[0314] The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is preferably 0.5 to 1.2 equivalents, and more preferably 0.7 to 1.1 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. By making the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used more than the aforementioned lower limit, it is possible to suppress the insufficient amount of unsaturated group introduced, and there is a tendency to make the subsequent reaction with polyacids and / or their anhydrides sufficient. By setting it below the aforementioned upper limit, it is possible to suppress the residue of unreacted products of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and there is a tendency to make the curing characteristics good.

[0315] Examples of the polyacid and / or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

[0316] Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

[0317] The addition reaction of the polyacid and / or its anhydride can be carried out using a known method, and the target product can be obtained by continuing the reaction under the same conditions as the addition reaction of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group and epoxy resin. The addition amount of the polyacid and / or its anhydride component is preferably an addition amount that makes the acid value of the generated carboxyl-containing epoxy (meth) acrylate resin become 10 to 150 mgKOH / g, and more preferably an addition amount that becomes 20 to 140 mgKOH / g. By setting it to above the aforementioned lower limit, there is a tendency for alkali developability to become good. By setting it to below the aforementioned upper limit, there is a tendency for curing performance to become good.

[0318] In the addition reaction of the polyacid and / or its anhydride, a polyfunctional alcohol (polyol) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, etc. can be added to introduce a multi-branched structure. At this time, there is no particular restriction on the mixing order of the polyacid and / or its anhydride and the polyfunctional alcohol. By heating, the polyacid and / or its anhydride and the epoxy resin and the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group and any hydroxyl group present in the mixture of the polyfunctional alcohol are subjected to an addition reaction.

[0319] By using a polyol, the molecular weight of the epoxy (meth) acrylate resin (C-2) can be increased, and a branched chain can be introduced into the molecule, which tends to achieve a balance between the molecular weight and the viscosity. In addition, the introduction rate of the acid group into the molecule can be increased, which tends to facilitate a balance between sensitivity and adhesion.

[0320] Examples of the carboxyl group-containing epoxy (meth)acrylate resin include, in addition to the above-described resins, resins described in Korean Patent Publication No. 10-2013-0022955.

[0321] The weight average molecular weight (Mw) of the carboxyl-containing epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is preferably 30000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 1500 to 15000, and further preferably 2000 to 15000. By setting it to above the aforementioned lower limit, there is a tendency to suppress the solubility in the developer from becoming too high. By setting it to below the aforementioned upper limit, there is a tendency to easily make the solubility in the developer good.

[0322] The acid value of the carboxyl-containing epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, 20 to 200 mgKOH / g is preferred, 60 to 150 mgKOH / g is more preferred, 80 to 130 mgKOH / g is further preferred, and 100 to 130 mgKOH / g is further preferred. By setting it to the above lower limit value or more, there is a tendency that the developing solubility is improved and the resolution becomes good. By setting it to the above upper limit value or less, there is a tendency that the residual film rate of the photosensitive coloring resin composition becomes high.

[0323] The chemical structure of the epoxy (meth)acrylate resin (C-2) is not particularly limited. From the viewpoint of developability, residual film rate and reliability, it is preferred to contain an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (C2-I) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C2-I)") and / or an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (C2-II) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C2-II)").

[0324] [Chemistry 16]

[0325]

[0326] In formula (C2-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bonding end.

[0327] The benzene ring in formula (C2-I) may be further substituted by any substituent.

[0328] [Chemistry 17]

[0329]

[0330] In formula (C2-II), R 13 Each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bonding end.

[0331] <Epoxy (meth)acrylate resin (C2-I)>

[0332] [Chemistry 18]

[0333]

[0334] In formula (C2-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bonding end.

[0335] The benzene ring in formula (C2-I) may be further substituted by any substituent.

[0336] (R 12 )

[0337] In the above formula (C2-I), R12 It represents a divalent hydrocarbon group which may have a substituent.

[0338] Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

[0339] The divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. From the viewpoint of development solubility, a linear aliphatic group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a cyclic aliphatic group is preferred. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and further preferably 6 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 1 to 10 are further preferred. By setting it to be above the aforementioned lower limit, a firm film is easily obtained, the surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion to the substrate to become good. By setting it to be below the aforementioned upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0340] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.

[0341] Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group as a side chain.

[0342] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 12 or less, more preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 12, more preferably 1 to 10, and further preferably 2 to 10. By setting it to be above the aforementioned lower limit, there is a tendency to form a firm film and improve the adhesion to the substrate. By setting it to be below the aforementioned upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency to improve the resolution.

[0343] Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a dicyclopentadiene ring, a dicyclopentane ring, etc. From the viewpoint of the rigidity of the skeleton, groups obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred.

[0344] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0345] As the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group can be mentioned. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 4 to 20, more preferably 5 to 15, and further preferably 6 to 10. By setting it to above the aforementioned lower limit, it is easy to obtain a firm film, it is not easy to produce surface roughness during development, and there is a tendency for the adhesion to the substrate to become good. By setting it to below the aforementioned upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0346] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0347] The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perylene ring, a quinazoline ring, a quinazolinone ring, and an azulene ring having two free atomic valencies.

[0348] From the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0349] Examples of the substituent that the divalent aromatic ring group may have include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. From the viewpoint of developer solubility, unsubstituted is preferred, and from the viewpoint of dispersibility and residual film rate, methyl and ethyl are preferred.

[0350] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked together include groups in which one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups are linked together.

[0351] The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, 1 to 3 are further preferred, and 2 to 3 are particularly preferred. By setting the number to be above the above lower limit, a strong film is easily obtained, the surface roughness generated during development is not easily generated, and there is a tendency for the adhesion to the substrate to become good. By setting the number to be below the above upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0352] The number of the divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits may be arbitrarily combined. For example, 1 to 10 are preferred, 1 to 5 are more preferred, 1 to 3 are further preferred, and 2 to 3 are particularly preferred. By setting the number to be above the above lower limit, a strong film is easily obtained, the surface roughness generated during development is not easily generated, and there is a tendency for the adhesion to the substrate to become good. By setting the number to be below the above upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0353] As a group formed by connecting one or more divalent aliphatic groups to one or more divalent aromatic ring groups, for example, groups represented by the following formulas (C2-IA) to (C2-IH) can be cited. In the following formulas (C2-IA) to (C2-IF), * represents a bonding end. From the viewpoint of the rigidity of the skeleton and the hydrophobization of the film, the group represented by the following formula (C2-IA) is preferred. In addition, from the viewpoint of dispersibility and residual film rate, the groups represented by the following formulas (C2-IG) and (C2-IH) are preferred.

[0354] [Chemistry 19]

[0355]

[0356] [Chemistry 20]

[0357]

[0358] In formula (C2-I), k represents 1 or 2. From the viewpoint of adhesion and platemaking properties, k is preferably 1. From the viewpoint of sensitivity and dispersibility, k is preferably 2. In addition, the epoxy (meth)acrylate resin (C2-I) may contain both a partial structure in which k is 1 and a partial structure in which k is 2.

[0359] The benzene ring in formula (C2-I) may be further substituted by any substituent.

[0360] As the substituent, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy can be mentioned. The number of substituents is not particularly limited, and can be 1 or more than 2. From the viewpoint of platemaking properties, it is preferably unsubstituted.

[0361] From the viewpoint of ease of synthesis, the partial structure represented by formula (C2-I) is preferably a partial structure represented by the following general formula (C2-I-1).

[0362] [Chemistry 21]

[0363]

[0364] In formula (C2-I-1), R 11 , R 12 and k has the same meaning as in formula (C2-I), R X represents a hydrogen atom or a polyacid residue, and * represents a bonding end.

[0365] The benzene ring in the formula (C2-I-1) may be further substituted by any substituent.

[0366] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid. Examples of the polyacid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0367] From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

[0368] The benzene ring in formula (C2-I-1) may be further substituted by any substituent. As the substituent, the substituents listed for the benzene ring in formula (C2-I) can be preferably used.

[0369] The partial structure represented by the formula (C2-I-1) contained in one molecule of the epoxy (meth)acrylate resin (C2-I) may be one or more. For example, R X The structure of hydrogen atom and R X The structures which are polyacid residues may exist in a mixed manner.

[0370] The number of partial structures represented by formula (C2-I) contained in one molecule of epoxy (meth) acrylate resin (C2-I) is not particularly limited, and is preferably 1 or more, more preferably 3 or more. In addition, it is preferably 20 or less, and more preferably 15 or less. The above upper and lower limits can be combined arbitrarily. It is preferably 1 to 20, more preferably 1 to 15, and more preferably 3 to 15. By setting it to be above the aforementioned lower limit, it is easy to obtain a firm film, and there is a tendency that surface roughness generated during development is not easily generated. By setting it to be below the aforementioned upper limit, the deterioration of sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0371] The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (C2-I) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, particularly preferably 4000 or more, and most preferably 5000 or more. In addition, it is preferably 30000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 1500 to 15000, and further preferably 2000 to 15000. By setting it to the above lower limit or more, there is a tendency for the residual film rate of the photosensitive coloring resin composition to be increased. By setting it to the above upper limit or less, there is a tendency for the solubility in the developer to be good.

[0372] The acid value of the epoxy (meth) acrylate resin (C2-I) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, 20 to 200 mgKOH / g is preferred, 60 to 150 mgKOH / g is more preferred, 80 to 130 mgKOH / g is further preferred, and 100 to 130 mgKOH / g is further preferred. By setting it to the above lower limit value or more, there is a tendency that the developing solubility is improved and the resolution becomes good. By setting it to the above upper limit value or less, there is a tendency that the residual film rate of the photosensitive coloring resin composition becomes high.

[0373] Specific examples of the epoxy (meth)acrylate resin (C2-I) are given below. In addition, * in the examples represents a bonding end.

[0374] [Chemistry 22]

[0375]

[0376] [Chemistry 23]

[0377]

[0378] [Chemistry 24]

[0379]

[0380] [Chemistry 25]

[0381]

[0382] [Chemistry 26]

[0383]

[0384] [Chemistry 27]

[0385]

[0386] <Epoxy (meth)acrylate resin (C2-II)>

[0387] [Chemistry 28]

[0388]

[0389] In formula (C2-II), R13 Each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bonding end.

[0390] From the viewpoint of light-emitting properties, the structure of formula (C2-II) is preferred.

[0391] (R 14 )

[0392] In formula (C2-II), R 14 It represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

[0393] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0394] The number of rings possessed by the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to be above the above lower limit, a strong film is easily obtained, and there is a tendency that the surface roughness generated during development is not easily generated. By setting it to be below the above upper limit, the deterioration of sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency to improve the resolution.

[0395] The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and further preferably 8 or more. In addition, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 4 to 30, further preferably 6 to 20, and particularly preferably 8 to 15. By setting it to be above the aforementioned lower limit, a strong film is easily obtained, and there is a tendency that the surface roughness generated during development is not easily generated. By setting it to be below the aforementioned upper limit, the deterioration of sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency that the resolution is improved.

[0396] Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the residual film rate and resolution of the photosensitive color resin composition, an adamantane ring is preferred.

[0397] The number of rings possessed by the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 4 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 4, further preferably 2 to 4, and particularly preferably 3 to 4. By setting it to be above the aforementioned lower limit, a strong film is easily obtained, and there is a tendency that surface roughness generated during development is not easily generated. By setting it to be below the aforementioned upper limit, the deterioration of sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency that the resolution is improved.

[0398] As the aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more. In addition, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 40 are more preferred, 8 to 30 are further preferred, 10 to 20 are further preferred, and 12 to 15 are particularly preferred. By setting it to above the aforementioned lower limit, it is easy to obtain a firm film, and there is a tendency that the surface roughness generated during development is not easy to occur. By setting it to below the aforementioned upper limit, there is a tendency that the patterning characteristics become good.

[0399] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, A fluorene ring is preferably a fluorene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, or a fluorene ring. From the viewpoint of patterning properties, a fluorene ring is preferred.

[0400] The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

[0401] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, a linear aliphatic group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a cyclic aliphatic group is preferred. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 6 or more. In addition, it is preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 25 are preferred, 3 to 20 are more preferred, and 6 to 15 are further preferred. By setting it to be above the aforementioned lower limit, a firm film is easily obtained, the surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion to the substrate to become good. By setting it to be below the aforementioned upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0402] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.

[0403] Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group as a side chain.

[0404] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, and is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to be above the aforementioned lower limit, there is a tendency to form a firm film and improve the adhesion to the substrate. In addition, by setting it to be below the aforementioned upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency to improve the resolution.

[0405] Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from an adamantane ring is preferred.

[0406] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0407] As the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group can be mentioned. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. In addition, it is preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15. By setting it to above the aforementioned lower limit, it is easy to obtain a firm film, it is not easy to produce surface roughness during development, and there is a tendency for the adhesion to the substrate to become good. By setting it to below the aforementioned upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0408] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0409] The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perylene ring, a quinazoline ring, a quinazolinone ring, and an azulene ring having two free atomic valencies. From the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0410] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of developing solubility, it is preferably unsubstituted.

[0411] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked together include groups in which one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups are linked together.

[0412] The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits may be arbitrarily combined. For example, 1 to 10 are preferred, 1 to 5 are more preferred, 1 to 3 are further preferred, and 2 to 3 are particularly preferred. By setting the number to be above the above lower limit, a strong film is easily obtained, the surface roughness generated during development is not easily generated, and there is a tendency for the adhesion to the substrate to become good. By setting the number to be below the above upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0413] The number of the divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits may be arbitrarily combined. For example, 1 to 10 are preferred, 1 to 5 are more preferred, 1 to 3 are further preferred, and 2 to 3 are particularly preferred. By setting the number to be above the above lower limit, a strong film is easily obtained, the surface roughness generated during development is not easily generated, and there is a tendency for the adhesion to the substrate to become good. By setting the number to be below the above upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0414] Examples of the group formed by connecting one or more divalent aliphatic groups to one or more divalent aromatic ring groups include the groups represented by the aforementioned formulae (C2-IA) to (C2-IF). From the perspective of the rigidity of the skeleton and the hydrophobization of the membrane, the group represented by the formula (C2-IC) is preferred.

[0415] The bonding method of the cyclic hydrocarbon group as a side chain relative to these divalent hydrocarbon groups is not particularly limited, and examples thereof include a method in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group as a side chain, and a method in which a cyclic hydrocarbon group as a side chain is constituted by including one carbon atom of an aliphatic group.

[0416] (R 15 , R 16 )

[0417] In formula (C2-II), R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent.

[0418] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, a linear aliphatic group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a cyclic aliphatic group is preferred. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 6 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 20 are preferred, 3 to 15 are more preferred, and 6 to 10 are further preferred. By setting it to be above the aforementioned lower limit, a firm film is easily obtained, the surface roughness generated during development is not easily generated, and there is a tendency for the adhesion to the substrate to become good. By setting it to be below the aforementioned upper limit, the deterioration of the sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency for the resolution to be improved.

[0419] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.

[0420] Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group as a side chain.

[0421] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. In addition, it is preferably 12 or less, and more preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 12, and more preferably 2 to 10. By setting it to be above the above lower limit, there is a tendency to form a firm film and improve substrate adhesion. By setting it to be below the above upper limit, the deterioration of sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency to improve resolution.

[0422] As the divalent cyclic aliphatic group, for example, there can be mentioned a group obtained by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a dicyclopentadiene ring. From the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferred.

[0423] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0424] (m, n)

[0425] In formula (C2-II), m and n each independently represent an integer of 0 to 2. When the lower limit is set to be above, the patterning adaptability becomes good, and there is a tendency that the surface roughness generated during development is not easily generated. In addition, when the upper limit is set to be below the upper limit, there is a tendency that the developability becomes good. From the viewpoint of developability, m and n are preferably 0. From the viewpoint of patterning adaptability and suppression of surface roughness generated during development, m and n are preferably 1 or more.

[0426] From the viewpoint of adhesion to the substrate, the partial structure represented by formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-1).

[0427] [Chemistry 29]

[0428]

[0429] In formula (C2-II-1), R 13 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer greater than or equal to 1, and * represents a bonding end. The benzene ring in formula (C2-II-1) may be further substituted with an arbitrary substituent.

[0430] (R α )

[0431] In formula (C2-II-1), R α It represents a monovalent cyclic hydrocarbon group which may have a substituent.

[0432] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0433] The number of rings possessed by the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to be above the above lower limit, it is easy to obtain a strong film, and there is a tendency that the surface roughness generated during development is not easy to occur. By setting it to be below the above upper limit, there is a tendency that the patterning characteristics become good.

[0434] The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and further preferably 8 or more. In addition, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 4 to 30, further preferably 6 to 20, and particularly preferably 8 to 15. By setting it to be above the above lower limit, it is easy to obtain a strong film, and there is a tendency that the surface roughness generated during development is not easy to occur. By setting it to be below the above upper limit, there is a tendency that the patterning characteristics become good.

[0435] Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.

[0436] The number of rings possessed by the aromatic ring group is not particularly limited, and is preferably 1 or more, preferably 2 or more, and more preferably 3 or more. In addition, it is preferably 10 or less, and more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. By setting it to be above the above lower limit, it is easy to obtain a strong film, and there is a tendency that the surface roughness generated during development is not easy to occur. By setting it to be below the above upper limit, there is a tendency that the patterning characteristics become good.

[0437] As the aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned. In addition, the number of carbon atoms in the aromatic ring group is not particularly limited, and is preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. In addition, it is preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15. By setting it to above the aforementioned lower limit, it is easy to obtain a firm film, and there is a tendency that the surface roughness generated during development is not easy to occur. By setting it to below the aforementioned upper limit, there is a tendency that the patterning characteristics become good.

[0438] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of development solubility, a fluorene ring is preferred.

[0439] Examples of substituents that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0440] p represents an integer greater than or equal to 1, and is preferably greater than or equal to 2. In addition, it is preferably less than or equal to 3. For example, it is preferably 1 to 3, and more preferably 2 to 3. When it is equal to or greater than the above lower limit, there is a tendency that the film curing degree and the residual film rate become higher. When it is equal to or less than the above upper limit, there is a tendency that the developability becomes good.

[0441] From the perspective of firm film curing, R α It is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

[0442] The benzene ring in formula (C2-II-1) may be further substituted by any substituent. As a substituent, for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group may be mentioned. The number of substituents is also not particularly limited, and may be 1 or more than 2.

[0443] From the viewpoint of patterning properties, no substitution is preferred.

[0444] Specific examples of the partial structure represented by formula (C2-II-1) are given below.

[0445] In the following examples, * indicates a bonding end.

[0446] [Chemistry 30]

[0447]

[0448] [Chemistry 31]

[0449]

[0450] [Chemistry 32]

[0451]

[0452] [Chemistry 33]

[0453]

[0454] [Chemistry 34]

[0455]

[0456] From the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane, the partial structure represented by the formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-2).

[0457] [Chemistry 35]

[0458]

[0459] In formula (C2-II-2), R 13 , R 15 , R16 , m and n have the same meanings as in formula (C2-II), R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bonding end.

[0460] The benzene ring in the formula (C2-II-2) may be further substituted by any substituent.

[0461] (R β )

[0462] In formula (C2-II-2), R β It represents a divalent cyclic hydrocarbon group which may have a substituent.

[0463] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0464] The number of rings possessed by the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 2 to 5. By setting it to be above the above lower limit, a strong film is easily obtained, and there is a tendency that the surface roughness generated during development is not easily generated. By setting it to be below the above upper limit, the deterioration of sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency to improve the resolution.

[0465] The number of carbon atoms of the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, and further preferably 8 or more. In addition, it is preferably 40 or less, more preferably 35 or less, and further preferably 30 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 6 to 35, and further preferably 8 to 30. By setting it to be above the above lower limit, there is a tendency to suppress the roughness of the film surface during development. By setting it to be below the above upper limit, the deterioration of sensitivity can be suppressed, the residual film rate after development is high, and there is a tendency to improve the resolution.

[0466] Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the residual film rate after development and the resolution, an adamantane ring is preferred.

[0467] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. Also, it is preferably 10 or less, and more preferably 5 or less.

[0468] The above upper and lower limits may be combined arbitrarily. For example, preferably 1 to 10, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. By setting the above lower limit value or more, a strong film is easily obtained, and there is a tendency that the surface roughness generated during development is not easily generated. By setting the above upper limit value or less, it is easy to suppress the deterioration of sensitivity or the reduction of film, and there is a tendency to improve the resolution.

[0469] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

[0470] The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and further preferably 10 or more. In addition, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits may be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 30 are more preferred, 8 to 20 are further preferred, and 10 to 15 are particularly preferred. By setting it to be above the above lower limit, it is easy to obtain a strong film, and there is a tendency that the surface roughness generated during development is not easy to occur. By setting it to be below the above upper limit, it is easy to suppress the deterioration of sensitivity or the reduction of film, and there is a tendency to improve the resolution.

[0471] As the aromatic ring in the aromatic ring group, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring can be cited. From the viewpoint of the residual film rate, a fluorene ring is preferred. Since the plane forming the fluorene ring is orthogonal to the bond connected to the two benzene rings, the volume becomes larger, thereby forming a more rigid skeleton, which is not easy to produce the penetration of the developer and the shrinkage during firing, and as a result, it is estimated that the residual film rate becomes higher.

[0472] Examples of substituents that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0473] From the viewpoint of suppressing film reduction and resolution, R β It is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. β It is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

[0474] The benzene ring in formula (C2-II-2) can be further substituted by any substituent. As a substituent, for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group can be mentioned. The number of the substituent is not particularly limited, and can be 1 or more than 2.

[0475] In addition, the two benzene rings may be connected via a substituent. Examples of the substituent in this case include -O-, -S-, -NH-, -CH 2 Equivalent divalent groups.

[0476] From the viewpoint of patterning properties, unsubstituted is preferred, while methyl substitution is preferred from the viewpoint of less likely to cause film reduction.

[0477] Specific examples of the partial structure represented by formula (C2-II-2) are given below.

[0478] In the following examples, * indicates a bonding end.

[0479] [Chemistry 36]

[0480]

[0481] [Chemistry 37]

[0482]

[0483] [Chemistry 38]

[0484]

[0485] [Chemistry 39]

[0486]

[0487] From the viewpoint of the coating film residual rate and patterning characteristics, the partial structure represented by formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-3).

[0488] [Chemistry 40]

[0489]

[0490] In formula (C2-II-3), R 13 , R 14 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), R Z represents a hydrogen atom or a polyacid residue.

[0491] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid. It should be noted that another OH group may be further removed to form a monovalent or divalent group with R Z That is, multiple formulas (C2-II-3) can be shared through R Z connect.

[0492] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0493] From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

[0494] The partial structure represented by the formula (C2-II-3) contained in one molecule of the epoxy (meth)acrylate resin (C2-II) may be one or more. For example, R Z The structure of hydrogen atom and R Z The structures which are polyacid residues may exist in mixture.

[0495] The number of partial structures represented by formula (C2-II) contained in one molecule of epoxy (meth) acrylate resin (C2-II) is not particularly limited, and is preferably 1 or more, more preferably 3 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 1 to 15, and further preferably 3 to 10. By setting it to be above the aforementioned lower limit, it is easy to obtain a firm film, and there is a tendency that surface roughness generated during development is not easily generated. By setting it to be below the aforementioned upper limit, it is easy to suppress the deterioration of sensitivity or film reduction, and there is a tendency to improve resolution.

[0496] The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (C2-II) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is preferably 10000 or less, more preferably 8000 or less, and further preferably 7000 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1000 to 10000, more preferably 1500 to 10000, further preferably 1500 to 8000, further preferably 2000 to 8000, and particularly preferably 2000 to 7000. By setting it to the above lower limit value or more, there is a tendency for the residual film rate of the photosensitive coloring resin composition to be higher. By setting it to the above upper limit value or less, there is a tendency for the solubility in the developer to be good.

[0497] The acid value of the epoxy (meth) acrylate resin (C2-II) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, 20 to 200 mgKOH / g is preferred, 60 to 150 mgKOH / g is more preferred, 80 to 130 mgKOH / g is further preferred, and 100 to 130 mgKOH / g is further preferred. By setting it to the above lower limit value or more, there is a tendency that the developing solubility is improved and the resolution becomes good. By setting it to the above upper limit value or less, there is a tendency that the residual film rate of the photosensitive coloring resin composition becomes high.

[0498] The epoxy (meth)acrylate resin (C-2) may be used alone or in combination of two or more.

[0499] <Acrylic Copolymer Resin (C-3)>

[0500] As the alkali-soluble resin (C), an acrylic copolymer resin (C-3) can be used from the viewpoint of compatibility with a pigment, a dispersant, etc. As the acrylic copolymer resin (C-3), for example, the resin described in Japanese Patent Application Laid-Open No. 2014-137466 can be preferably used.

[0501] Examples of the acrylic copolymer resin (C-3) include copolymers of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (C3-1)") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as "unsaturated monomer (C3-2)").

[0502] Examples of the unsaturated monomer (C3-1) include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloxyalkyl] esters of polycarboxylic acids with a valence of 2 or more such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends such as ω-carboxy polycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

[0503] These unsaturated monomers (C3-1) can be used alone or in combination of two or more.

[0504] Examples of the unsaturated monomer (C3-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

[0505] Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

[0506] Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] decane-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane and the like (meth)acrylates;

[0507] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 2,6 ] vinyl ethers such as decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane;

[0508] A macromonomer having a mono(meth)acryloyl group at the end of a polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

[0509] These unsaturated monomers (C3-2) can be used alone or in combination of two or more.

[0510] In the copolymer of the unsaturated monomer (C3-1) and the unsaturated monomer (C3-2), the copolymerization ratio of the unsaturated monomer (C3-1) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (C3-1) within such a range, there is a tendency to obtain a photosensitive coloring resin composition having excellent alkali developability and storage stability.

[0511] Examples of the copolymer of the unsaturated monomer (C3-1) and the unsaturated monomer (C3-2) include copolymers disclosed in JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, and JP-A-2004-101728.

[0512] The copolymer of the unsaturated monomer (C3-1) and the unsaturated monomer (C3-2) can be produced by a known method, and its structure, Mw, and Mw / Mn (Mn is the number average molecular weight) can also be controlled by the method disclosed in, for example, Japanese Patent Publication No. 2003-222717, Japanese Patent Publication No. 2006-259680, and International Publication No. 2007 / 029871.

[0513] As the acrylic copolymer resin (C-3), in addition to the above, resins described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 can also be used.

[0514] <(D) Photopolymerization Initiator>

[0515] The photosensitive coloring composition of the present invention contains (D) a photopolymerization initiator.

[0516] (D) The photopolymerization initiator is a component that directly absorbs light to initiate a decomposition reaction or a dehydrogenation reaction to generate polymerization-active radicals. A polymerization accelerator (chain transfer agent), a sensitizing dye, or other additive may be added as needed.

[0517] As the photopolymerization initiator, for example, there can be mentioned the metallocene compounds including the titanocene compounds described in Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197; the hexaarylbiimidazole derivatives described in Japanese Patent Publication No. 2000-56118; the halogenated methylated oxadiazole derivatives, halogenated methyl-s-triazine derivatives, and α-aminoalkylphenone derivatives described in Japanese Patent Publication No. 10-39503; and the oxime ester compounds described in Japanese Patent Publication No. 2000-80068 and Japanese Patent Publication No. 2006-36750.

[0518] Examples of the metallocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl)titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl)titanium, dicyclopentadienyl bis(2,6-difluorophenyl)titanium, dicyclopentadienyl bis(2,4-difluorophenyl)titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, di(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and dicyclopentadienyl [2,6-difluoro-3-(pyrrol-1-yl)-phenyl]titanium.

[0519] Examples of 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, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0520] Examples of the halogenated methylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-3,4-oxadiazole.

[0521] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0522] Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

[0523] As the (D) photopolymerization initiator, oxime ester compounds are particularly effective from the perspective of sensitivity and platemaking properties. For example, when an alkali-soluble resin is used, such oxime ester compounds with excellent sensitivity are particularly useful. Oxime ester compounds have a high quantum yield in the photoreaction and high activity of the generated free radicals, so they have high sensitivity and are stable to thermal reactions, and a highly sensitive photosensitive colored resin composition can be obtained in a small amount.

[0524] Examples of the oxime ester compound include compounds represented by the following general formula (IV).

[0525] [Chemistry 41]

[0526]

[0527] In formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0528] R 21b represents an arbitrary substituent including an aromatic ring.

[0529] R 22a It represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent.

[0530] n represents an integer of 0 or 1.

[0531] R 21a The number of carbon atoms in the alkyl group is not particularly limited. From the viewpoint of solubility in a solvent and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 2 to 15, and further preferably 2 to 10. For example, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl.

[0532] Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl, and N-acetyl-N-acetoxyamino. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0533] As R 21aThe aromatic ring group in the photosensitive colored resin composition may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive colored resin composition. In addition, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 5 to 30, more preferably 5 to 20, and further preferably 5 to 12.

[0534] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0535] Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group formed by connecting these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group formed by connecting these substituents are preferred, and a connected alkoxy group is more preferred.

[0536] From the viewpoint of developability, R 21a It is an aromatic ring group which may have a substituent, and is more preferably an aromatic ring group having an alkoxy group connected to the substituent.

[0537] As R 21b , may be a substituted carbazolyl group, a substituted thioxanthone group, a substituted diphenyl sulfide group, a substituted fluorenyl group or a substituted indolyl group. From the viewpoint of sensitivity, a substituted carbazolyl group is preferred. From the viewpoint of electrical reliability, a substituted diphenyl sulfide group is preferred.

[0538] R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but is preferably 2 or more, preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and particularly preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. Examples of the alkanoyl group include acetyl, propionyl, and butyryl.

[0539] Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0540] R 22a The number of carbon atoms of the aromatic acyl group in is not particularly limited, but is preferably 7 or more, more preferably 8 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less from the viewpoint of solubility in a solvent and sensitivity. Examples of the aromatic acyl group include benzoyl and naphthoyl.

[0541] Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0542] From the viewpoint of sensitivity, R 22a It is an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and still more preferably an acetyl group.

[0543] As the (D) photopolymerization initiator, for example, Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 200 Photopolymerization initiators described in International Publication No. 5 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, International Publication No. 2012 / 68879, and Japanese Patent Application Publication No. 2016-133574.

[0544] The photopolymerization initiator may be used alone or in combination of two or more.

[0545] The photopolymerization initiator may be mixed with a sensitizing dye or a polymerization accelerator according to the wavelength of the image exposure light source, if necessary, for the purpose of improving the sensitivity. Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Laid-Open Nos. 4-221958 and 4-219756, coumarin dyes having a heterocyclic ring described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335, 3-ketocoumarin compounds described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335, pyrromethene dyes described in Japanese Patent Laid-Open No. 6-19240, and 47-2528 and 54-155292. The pigment having a dialkylaminobenzene skeleton described in Japanese Patent Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818.

[0546] As the sensitizing dye, a sensitizing dye containing an amino group is preferred, and a compound having an amino group and a phenyl group in the same molecule is more preferred. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone are preferred; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4 Preferably, the compound containing p-dialkylaminophenyl group is oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, and the like, and 4,4'-dialkylaminobenzophenone is particularly preferred.

[0547] The sensitizing dye may be used alone or in combination of two or more.

[0548] As the polymerization accelerator, for example, aromatic amines such as 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate, and mercapto compounds described below can be used.

[0549] The polymerization accelerator may be used alone or in combination of two or more.

[0550] <(E) Ethylenically Unsaturated Compound>

[0551] The photosensitive colored resin composition of the present invention contains (E) an ethylenically unsaturated compound. By containing (E) an ethylenically unsaturated compound, there is a tendency for the sensitivity to be improved.

[0552] The (E) ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Examples of the (E) ethylenically unsaturated compound include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters of polyhydric or monohydric alcohols.

[0553] In the present invention, it is particularly preferred to use a multifunctional ethylenic monomer having two or more ethylenic unsaturated groups in one molecule. The number of ethylenic unsaturated groups possessed by the multifunctional ethylenic monomer is not particularly limited, and is preferably more than 2, more preferably more than 4, and further preferably more than 5, and further preferably less than 8, and more preferably less than 7. The above upper and lower limits can be combined arbitrarily. For example, preferably 2 to 8, more preferably 2 to 7, further preferably 4 to 7, and particularly preferably 5 to 7. By setting it to above the aforementioned lower limit, there is a tendency to become highly sensitive. In addition, by setting it to below the aforementioned upper limit, there is a tendency to improve solubility in solvents.

[0554] Examples of the polyfunctional ethylenic monomer include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polyvalent carboxylic acids.

[0555] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylates of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylates in which these acrylates are replaced by methacrylates; itaconates in which these acrylates are replaced by itaconates; crotonates in which these acrylates are replaced by crotonates; and maleates in which these acrylates are replaced by maleates.

[0556] Examples of the esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0557] The esters obtained by the esterification reaction of polycarboxylic acids and unsaturated carboxylic acids with polyhydroxy compounds are not necessarily single substances, and examples thereof include: condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol and glycerol.

[0558] In addition, examples of the polyfunctional olefinic monomer used in the present invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl-containing compounds such as divinyl phthalate.

[0559] Examples of the urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), and UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).

[0560] From the viewpoint of curability, as the (E) ethylenically unsaturated compound, it is preferred to use urethane (meth)acrylates obtained by reacting an alkyl (meth)acrylate, a polyisocyanate compound and a hydroxyl-containing (meth)acrylate, or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate, and it is more preferred to use a polyisocyanate compound and a hydroxyl-containing (meth)acrylate.

[0561] These may be used alone or in combination of two or more.

[0562] <Other ingredients of the photosensitive coloring resin composition>

[0563] The photosensitive colored resin composition of the present invention may contain, in addition to the above components, additives such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors.

[0564] (1) Adhesion enhancer

[0565] The photosensitive colored resin composition of the present invention may contain an adhesion improver in order to improve adhesion to a substrate. As the adhesion improver, a silane coupling agent or a phosphoric acid group-containing compound is preferred.

[0566] As the silane coupling agent, for example, various silane coupling agents such as epoxy-based, (meth)acrylic-based, and amino-based silane coupling agents may be used alone or in combination of two or more.

[0567] Examples of the silane coupling agent include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, and isocyanatesilanes such as 3-isocyanatepropyltriethoxysilane. Epoxysilane-based silane coupling agents are particularly preferred.

[0568] As the phosphoric acid group-containing compound, a (meth)acryloyl group-containing phosphoric acid ester is preferred, and a compound represented by the following general formula (g1), (g2) or (g3) is preferred.

[0569] [Chemistry 42]

[0570]

[0571] In formula (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.

[0572] These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

[0573] (2) Surfactants

[0574] The photosensitive color resin composition of the present invention may contain a surfactant in order to improve coating properties.

[0575] As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Nonionic surfactants are preferably used because they have little influence on various properties, and fluorine-based and silicone-based surfactants are more preferred because of their coating properties.

[0576] Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Daikin Co., Ltd.), L-77 (manufactured by Unicar Japan Co., Ltd.), and FC4430 (manufactured by 3M Co., Ltd.).

[0577] The surfactant may be used alone or in combination of two or more.

[0578] (3) Pigment derivatives

[0579] The photosensitive color resin composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.

[0580] Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine derivatives, with phthalocyanine and quinophthalone derivatives being preferred.

[0581] Examples of substituents of the pigment derivative include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups, which are substituents directly or via alkyl groups, aryl groups, and heterocyclic groups, and are preferably sulfonic acid groups. Multiple substituents may be substituted on one pigment skeleton, or multiple substituents may be substituted.

[0582] Examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.

[0583] (4) Thiol compounds

[0584] Furthermore, in order to improve the adhesion to the substrate, a mercapto compound may be contained as a polymerization accelerator.

[0585] Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, tris ... pentaerythrit Thiol compounds having a heterocyclic ring, such as 1,4-bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and aliphatic polyfunctional thiol compounds. These may be used alone or in combination of two or more.

[0586] (5) Inhibitor

[0587] The photosensitive colored resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. The polymerization inhibitor inhibits radical polymerization of the lower layer of the coating film, and thus is considered to control the taper angle (the angle between the support and the cured product in the cross section of the cured product).

[0588] Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-methylphenol is preferred. From the viewpoint of particularly excellent working environment, hydroquinone monomethyl ether and methyl hydroquinone are preferred.

[0589] The polymerization inhibitor may be used alone or in combination of two or more.

[0590] When producing (C) an alkali-soluble resin, a polymerization inhibitor may be contained in the alkali-soluble resin. The polymerization inhibitor in the resin may be used as the polymerization inhibitor of the present invention. In addition to the polymerization inhibitor, the same or different polymerization inhibitor may be added to the resin when producing the photosensitive coloring resin composition.

[0591] When the photosensitive color resin composition includes a polymerization inhibitor, the content ratio thereof is not particularly limited, and is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.01% by mass or more, relative to the total solid content of the photosensitive color resin composition. In addition, it is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and further preferably 0.1% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 0.0005% by mass to 0.3% by mass, more preferably 0.001% by mass to 0.2% by mass, and further preferably 0.01% by mass to 0.1% by mass. By setting it to above the aforementioned lower limit, there is a tendency to be able to control the shape of the cured product. By setting it to below the aforementioned upper limit, there is a tendency to be able to maintain the necessary sensitivity.

[0592] (6) Solvent

[0593] The photosensitive colored resin composition of the present invention preferably contains a solvent. By containing a solvent, the colorant can be dispersed or dissolved in the solvent, and coating becomes easy.

[0594] The photosensitive colored resin composition of the present invention is used in a state where (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, (E) an ethylenically unsaturated compound, and other various materials used as needed are dissolved or dispersed in a solvent. From the viewpoint of dispersibility and coating properties, an organic solvent is preferred.

[0595] From the viewpoint of coating properties, an organic solvent having a boiling point of 100 to 300° C. is preferred, and an organic solvent having a boiling point of 120 to 280° C. is more preferred. The boiling point referred to here means the boiling point at a pressure of 1013.25 hPa, and all the following boiling points are the same.

[0596] Examples of the organic solvent include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and tripropylene glycol methyl ether;

[0597] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0598] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0599] Glycol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate;

[0600] Alkyl acetates such as cyclohexanol acetate;

[0601] Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

[0602] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0603] Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0604] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0605] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0606] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0607] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone;

[0608] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0609] Halogenated hydrocarbons such as butyl chloride and amyl chloride;

[0610] Ether ketones such as methoxymethylpentyl ketone;

[0611] Nitriles such as acetonitrile and benzonitrile.

[0612] As commercially available organic solvents, for example, mineral spirits, VARSOL #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (all trade names) can be used.

[0613] These organic solvents may be used alone or in combination of two or more.

[0614] When forming the partition wall by photolithography, an organic solvent having a boiling point of 100 to 240°C is preferred, an organic solvent having a boiling point of 120 to 200°C is more preferred, and an organic solvent having a boiling point of 120 to 170°C is further preferred.

[0615] Glycol alkyl ether acetates are preferred because they have a good balance between coating properties and surface tension and have high solubility of components in the composition.

[0616] The glycol alkyl ether acetates may be used alone or in combination of two or more.

[0617] Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are preferred. Propylene glycol monomethyl ether is preferred in view of the solubility of the components in the composition.

[0618] The polarity of glycol monoalkyl ethers is high. When the amount added is too large, the pigment is easily aggregated, and there is a tendency that the storage stability of the photosensitive color resin composition obtained later, such as the viscosity of the photosensitive color resin composition, is reduced. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.

[0619] By using an organic solvent having a boiling point of 150°C or more (hereinafter sometimes referred to as a "high boiling point solvent") in combination, the photosensitive colored resin composition becomes difficult to dry. Since it has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed due to rapid drying, a high boiling point solvent can be used in combination. For example, it has the effect of preventing foreign matter defects caused by the precipitation and solidification of the colorant at the front end of the slit nozzle. From the viewpoint of such a high effect, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are preferred as high boiling point solvents used in combination.

[0620] When a high boiling point solvent is used in combination, the content of the high boiling point solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. By setting it above the aforementioned lower limit, there is a tendency to suppress, for example, the precipitation and solidification of colorants at the front end of the slit nozzle to cause foreign matter defects. By setting it below the aforementioned upper limit, there is a tendency to suppress the drying time of the composition from becoming longer, and to suppress problems such as poor production rhythm of the reduced pressure drying process and pin marks of pre-baking.

[0621] The high boiling point solvent may be glycol alkyl ether acetate or glycol alkyl ether. In this case, the high boiling point solvent may not be contained separately.

[0622] Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glycerol triacetate.

[0623] <Content Ratio of Each Component in the Photosensitive Coloring Resin Composition>

[0624] The content ratio of the colorant (A) in the photosensitive colored resin composition of the present invention is not particularly limited, and is preferably 10% by mass or more, more preferably 15% by mass or more, relative to the total solid content of the photosensitive colored resin composition. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 10 to 50% by mass, more preferably 15 to 40% by mass, further preferably 15 to 30% by mass, and further preferably 15 to 20% by mass. By setting it to above the aforementioned lower limit, there is a tendency to ensure light-shielding properties. By setting it to below the aforementioned upper limit, there is a tendency to reduce the amount of dispersants and suppress surface roughness.

[0625] When the photosensitive color resin composition contains an organic coloring pigment, the content ratio thereof is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more, relative to the total solid content of the photosensitive color resin composition. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less. For example, 10 to 50% by mass is preferred, 15 to 40% by mass is more preferred, 20 to 30% by mass is further preferred, and 20 to 25% by mass is particularly preferred. By setting it to above the aforementioned lower limit, there is a tendency for the light-shielding property to become higher. By setting it to below the aforementioned upper limit, there is a tendency to reduce the amount of dispersant and to suppress surface roughness.

[0626] In the case where (A) colorant includes red pigment and / or orange pigment, the total content ratio of red pigment and orange pigment is not particularly limited, and relative to the total mass of (A) colorant, it is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more. In addition, it is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. For example, it is preferably 5-40% by mass, more preferably 8-40% by mass, further preferably 10-30% by mass, and particularly preferably 12-20% by mass. By setting it to above the aforementioned lower limit, there is a tendency to form a hue close to black. By setting it to below the aforementioned upper limit, there is a tendency to become highly sensitive.

[0627] When (A) colorant includes blue pigment and / or purple pigment, the total content ratio of blue pigment and purple pigment is not particularly limited, and relative to the total mass of (A) colorant, it is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. In addition, it is preferably 95% by mass or less, more preferably 92% by mass or less, and particularly preferably 90% by mass or less. For example, it is preferably 30-95% by mass, more preferably 50-95% by mass, further preferably 70-92% by mass, and particularly preferably 80-90% by mass. By setting it to above the aforementioned lower limit, there is a tendency to form a hue close to black. By setting it to below the aforementioned upper limit, there is a tendency for sensitivity and light-shielding properties to become good.

[0628] In the case where the colorant (A) includes both red pigment and / or orange pigment, and blue pigment and / or purple pigment, the content ratio of the red pigment and / or orange pigment relative to 100 parts by mass of the content of the blue pigment and / or purple pigment is not particularly limited, preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 8 parts by mass or more. In addition, preferably 300 parts by mass or less, more preferably 100 parts by mass or less, particularly preferably 50 parts by mass or less. For example, preferably 1 to 300 parts by mass, more preferably 3 to 100 parts by mass, further preferably 5 to 100 parts by mass, and particularly preferably 8 to 50 parts by mass. By setting it to above the aforementioned lower limit, there is a tendency to suppress the transmission of blue light and the light-shielding property to be higher. By setting it to below the aforementioned upper limit, there is a tendency to be able to form a hue close to black.

[0629] When the photosensitive coloring resin composition contains an organic black pigment, the content ratio thereof is not particularly limited, and is preferably 10% by mass or more, more preferably 15% by mass or more, relative to the total solid content of the photosensitive coloring resin composition. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 10 to 50% by mass, more preferably 15 to 40% by mass, further preferably 15 to 30% by mass, and further preferably 15 to 20% by mass. By setting it to above the aforementioned lower limit, there is a tendency to ensure light-shielding properties. By setting it to below the aforementioned upper limit, there is a tendency to reduce the amount of dispersants and to suppress surface roughness.

[0630] When the photosensitive color resin composition contains an organic black pigment represented by the general formula (A-1-1), the content ratio thereof is not particularly limited, and is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more, relative to the total solid content of the photosensitive color resin composition. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. For example, 3 to 50% by mass is preferred, 5 to 40% by mass is more preferred, 10 to 30% by mass is further preferred, and 20 to 30% by mass is particularly preferred. By setting it to the above lower limit value or more, there is a tendency for the light-shielding property to become higher. If it is below the above upper limit value, there is a tendency to reduce the amount of dispersant and to suppress surface roughness.

[0631] When the photosensitive coloring resin composition includes carbon black as an inorganic black pigment, the content ratio is not particularly limited, and is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more relative to the total solid content of the photosensitive coloring resin composition. In addition, it is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. For example, it is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 3 to 10% by mass. By setting it to above the aforementioned lower limit, there is a tendency for the light-shielding property to become higher. By setting it to below the aforementioned upper limit, there is a tendency to form a cured product with high resistance and low dielectric constant.

[0632] In the case where (A) colorant includes black pigment and organic coloring pigment, the total content ratio thereof is not particularly limited, and relative to the total mass of (A) colorant, the content ratio of black pigment is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and particularly preferably 70% by mass or more. In addition, it is usually 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. For example, preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and further preferably 30 to 100% by mass. By setting it to above the aforementioned lower limit, the light-shielding property becomes higher, and there is a tendency to form a hue close to black. By setting it to below the aforementioned upper limit, the residue during development decreases, and there is a tendency for the reliability during the production of the element to become good.

[0633] (B) The content ratio of the dispersant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more, relative to the total solid content of the photosensitive coloring resin composition. In addition, it is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and further preferably 7% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, further preferably 3 to 10% by mass, and particularly preferably 3 to 7% by mass. By setting it to above the aforementioned lower limit, there is a tendency to easily obtain sufficient dispersibility. By setting it to below the aforementioned upper limit, there is a tendency to reduce the generation of smoke.

[0634] The content ratio of (B) dispersant relative to 100 parts by mass of (A) colorant is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. In addition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 15 to 30 parts by mass. By setting it to above the aforementioned lower limit, there is a tendency to easily obtain sufficient dispersibility. By setting it to below the aforementioned upper limit, there is a tendency to reduce the generation of smoke.

[0635] (C) The content ratio of the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total solid content of the photosensitive coloring resin composition. In addition, it is preferably 85% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 55% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, further preferably 30 to 60% by mass, further preferably 30 to 55% by mass, and particularly preferably 40 to 55% by mass. By setting it to the above lower limit or more, there is a tendency to suppress the reduction of solubility of the unexposed part in the developer and suppress poor development. By setting it to the above upper limit or less, there is a tendency to maintain appropriate sensitivity and reduce smoke generation. In addition, the dissolution of the exposed part caused by the developer can be suppressed, and there is a tendency to optimize the residual film rate and reduce the cone angle.

[0636] The content ratio of the alkali-soluble resin (C-1) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total solid content of the photosensitive coloring resin composition. In addition, it is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, further preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass. By setting it to above the aforementioned lower limit, there is a tendency to reduce the generation of smoke. By setting it to below the aforementioned upper limit, there is a tendency for the residual film rate to be optimized and the cone angle to be lowered.

[0637] (C) The content ratio of the alkali-soluble resin (C-1) in the alkali-soluble resin is not particularly limited, and is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. In addition, it is usually 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 90% by mass, more preferably 20 to 90% by mass, further preferably 30 to 80% by mass, further preferably 40 to 80% by mass, and particularly preferably 60 to 80% by mass. By setting it to above the aforementioned lower limit, there is a tendency to reduce the generation of smoke. By setting it to below the aforementioned upper limit, there is a tendency for the residual film rate to be optimized and the cone angle to be lowered.

[0638] When the photosensitive color resin composition of the present invention contains an epoxy (meth) acrylate resin (C-2), the content ratio of the epoxy (meth) acrylate resin (C-2) is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more relative to the total solid content of the photosensitive color resin composition of the present invention. In addition, it is preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 5 to 80% by mass, more preferably 10 to 70% by mass, more preferably 20 to 60% by mass, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass. By setting it to the above lower limit value or more, there is a tendency that the residual film rate is optimized and the taper angle becomes lower. By setting it to the above upper limit value or less, there is a tendency that smoke generation can be reduced.

[0639] When the (C) alkali-soluble resin includes an epoxy (meth) acrylate resin (C-2), the content ratio of the epoxy (meth) acrylate resin (C-2) contained in the (C) alkali-soluble resin is not particularly limited, and is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. In addition, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 10 to 60% by mass, more preferably 30 to 50% by mass, and further preferably 20 to 40% by mass. By setting it to above the aforementioned lower limit, there is a tendency for the residual film rate to be optimized and the cone angle to be lowered. By setting it to below the aforementioned upper limit, there is a tendency to reduce the generation of smoke.

[0640] When the photosensitive colored resin composition contains an epoxy (meth) acrylate resin (C-2), the content ratio of the epoxy (meth) acrylate resin (C-2) in the (C) alkali-soluble resin relative to 100 parts by mass of the alkali-soluble resin (C-1) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more. In addition, it is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 50 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 10 to 80 parts by mass, more preferably 20 to 60 parts by mass, and further preferably 30 to 50 parts by mass. By setting it to above the aforementioned lower limit, there is a tendency for the residual film rate to be optimized and the cone angle to be lowered. By setting it to below the aforementioned upper limit, there is a tendency to reduce the generation of smoke.

[0641] (D) The content ratio of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more, relative to the total solid content of the photosensitive colored resin composition of the present invention. In addition, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and particularly preferably 6% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, further preferably 1 to 10% by mass, further preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass. By setting it to above the aforementioned lower limit, there is a tendency to suppress the decrease in sensitivity. By setting it to below the aforementioned upper limit, there is a tendency to suppress the decrease in solubility of the unexposed portion in the developer and suppress poor development.

[0642] When a polymerization accelerator is used together with the photopolymerization initiator (D), the content ratio of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more relative to the total solid content of the photosensitive color resin composition of the present invention. In addition, it is preferably 10% by mass or less, and more preferably 5% by mass or less. For example, it is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass.

[0643] In addition, the polymerization accelerator is preferably used in a ratio of 0.1 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (D). By making the content ratio of the polymerization accelerator greater than the aforementioned lower limit, there is a tendency to suppress the decrease in sensitivity to exposure light. By setting it below the aforementioned upper limit, there is a tendency to suppress the decrease in solubility of the unexposed portion in the developer and suppress poor development.

[0644] When a sensitizing dye is used together with the (D) photopolymerization initiator, the content ratio of the sensitizing dye is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, relative to the total solid content in the photosensitive color resin composition from the viewpoint of sensitivity.

[0645] When the photosensitive colored resin composition of the present invention contains (E) an ethylenically unsaturated compound, the content ratio of the (E) ethylenically unsaturated compound is not particularly limited, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more relative to the total solid content of the photosensitive colored resin composition of the present invention. In addition, it is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 30% by mass, more preferably 5 to 25% by mass, further preferably 10 to 25% by mass, and particularly preferably 15 to 20% by mass. By setting it to above the aforementioned lower limit, there is a tendency that the appropriate sensitivity can be maintained, the dissolution of the exposed portion caused by the developer is suppressed, and the clarity and adhesion of the pattern can be suppressed. By setting it to below the aforementioned upper limit, there is a tendency that the permeability of the developer to the exposed portion is suppressed and it is easy to obtain a good image.

[0646] The content ratio of the (C) alkali-soluble resin in the photosensitive colored resin composition of the present invention relative to 100 parts by mass of the (E) ethylenically unsaturated compound is not particularly limited, but is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, further preferably 250 parts by mass or more, further preferably 300 parts by mass or more, and particularly preferably 350 parts by mass or more. In addition, it is preferably 700 parts by mass or less, more preferably 500 parts by mass or less, further preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 100 to 700 parts by mass, more preferably 200 to 700 parts by mass, further preferably 250 to 500 parts by mass, further preferably 300 to 500 parts by mass, and particularly preferably 300 to 400 parts by mass. By setting it to the above lower limit value or more, there is a tendency to become an appropriate dissolution development state without peeling, etc. By setting it to the above upper limit value or less, there is a tendency to obtain an appropriate dissolution time relative to the developer.

[0647] When a close adhesion improving agent is used, its content ratio is not particularly limited, but is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and further preferably 0.4 to 2% by mass relative to the total solid content of the photosensitive coloring resin composition. By setting it to be above the above lower limit, there is a tendency that the close adhesion improving effect can be sufficiently obtained. By setting it to be below the above upper limit, there is a tendency that the sensitivity can be reduced or the residue remaining after development can be suppressed to become a defect.

[0648] When a surfactant is used, the content ratio thereof is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.005 to 1% by mass, further preferably 0.01 to 0.5% by mass, and particularly preferably 0.03 to 0.3% by mass relative to the total solid content of the photosensitive coloring resin composition. By setting the content to be above the lower limit, there is a tendency that the smoothness and uniformity of the coating film are easily expressed. By setting the content to be below the upper limit, there is a tendency that the smoothness and uniformity of the coating film are easily expressed, and the deterioration of other characteristics can also be suppressed.

[0649] The photosensitive colored resin composition of the present invention can be adjusted by using a solvent so that the content ratio of the total solid content is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the liquid can be adjusted in a manner preferably of 5 to 50% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass.

[0650] <Smoke Volume>

[0651] The smoke amount in the present invention refers to the ratio (%) obtained by dividing the weight reduction of the coating film before and after firing by the weight of the coating film before firing when the coating film obtained by coating, drying and exposing the photosensitive resin composition is subjected to heat curing treatment (firing). Specifically, the photosensitive resin composition is coated on a support by the method described below, dried, exposed, and optionally developed to prepare a substrate before firing. Then, its weight is measured. Thereafter, firing is performed to prepare a substrate after firing (a substrate for measuring the smoke amount). The weight of the substrate after firing is measured. The smoke amount is calculated from the weight before and after firing.

[0652] The smoke in the present invention refers to components generated from a coating film obtained by coating, drying and exposing the photosensitive resin composition and firing the coating film, and includes thermal decomposition components obtained by firing the components contained in the photosensitive resin composition, unreacted low molecular components, and the like.

[0653] <Physical Properties of Photosensitive Colored Resin Composition>

[0654] In the photosensitive colored resin composition of the present invention, the optical density (OD) per 1 μm film thickness of the coating obtained by curing the photosensitive colored resin composition is 0.5 or more. Preferably it is 0.7 or more, more preferably 0.9 or more, and preferably 4.0 or less, more preferably 3.0 or less, further preferably 2.0 or less, and particularly preferably 1.5 or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 0.5 to 4.0, 0.5 to 3.0, 0.7 to 2.0, or 0.9 to 1.5. By setting it to above the aforementioned lower limit, there is a tendency to obtain sufficient light-shielding properties. By setting it to below the aforementioned upper limit, there is a tendency to suppress the surface roughness of the electrode.

[0655] The optical density (OD) per 1 μm film thickness of the coating film may be measured using a coating film obtained by curing the photosensitive color resin composition of the present invention, and can be measured using a coating film having a film thickness of 0.5 to 1.5 μm after heat curing at 230° C. for 20 minutes, and converted into an optical density per 1 μm film thickness.

[0656] Optical density refers to the transmitted optical density represented by the ISO visual density in the ISO 5-3 standard, which is the spectral sensitivity characteristic of the light receiving part. Usually, the A light source specified by CIE (International Commission on Illumination) is used as the light source. As a measuring instrument that can be used to measure the transmitted optical density, for example, X-Rite 361T (V) of Sakata Inx Engineering Co., Ltd. can be cited.

[0657] <Method for producing photosensitive colored resin composition>

[0658] The photosensitive coloring resin composition of the present invention is produced by a conventional method, for example, by mixing the components contained in the photosensitive coloring composition with a stirrer.

[0659] The colorant (A) is preferably dispersed in advance using a paint conditioner, sand mill, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. The dispersion treatment can finely divide the colorant (A) into microparticles, thereby improving the coating properties of the photosensitive color resin composition.

[0660] The dispersion treatment is preferably performed in a system using (A) a colorant, (B) a dispersant, and a solvent in combination, or in a system using part or all of (C) an alkali-soluble resin in combination (hereinafter, the composition obtained by the dispersion treatment is also referred to as a "pigment dispersion"). In particular, when a polymer dispersant is used as the (B) dispersant, the viscosity increase over time of the obtained pigment dispersion and photosensitive color resin composition is suppressed, that is, the dispersion stability is excellent, which is preferred.

[0661] In this way, in the step of producing the photosensitive colored resin composition, it is preferred to produce a pigment dispersion containing at least (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and a solvent.

[0662] As the (A) colorant, (B) dispersant, (C) alkali-soluble resin and solvent that can be used in the pigment dispersion, the substances described as substances that can be used in the photosensitive color resin composition can be preferably used. As the content ratio of each colorant in the (A) colorant in the pigment dispersion, the content ratio described as the content ratio in the photosensitive color resin composition can be preferably used.

[0663] When a liquid containing all the components of the photosensitive color resin composition is dispersed, the heat generated during the dispersion treatment may cause the highly reactive components to be modified. Therefore, the dispersion treatment is preferably performed in a system containing a dispersant (B).

[0664] When dispersing the colorant (A) with a sand mill, it is preferred to use glass beads or zirconia beads with a particle size of about 0.1 to 8 mm. The dispersion treatment conditions are preferably 0°C to 100°C, more preferably room temperature to 80°C. The dispersion time varies depending on the composition of the liquid and the size of the dispersion treatment device, so it is adjusted appropriately. The goal of dispersion is to control the gloss of the pigment dispersion so that the 20-degree specular gloss (JIS Z8741) of the photosensitive coloring resin composition is in the range of 50 to 300. When the gloss of the photosensitive coloring resin composition is low, the dispersion treatment is insufficient, and most of the coarse pigment (colorant) particles remain, and the developability, adhesion, resolution, etc. may become insufficient. If the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is broken and a large amount of ultrafine particles are produced, so there is a tendency for the dispersion stability to be impaired.

[0665] The dispersed particle size of the pigment dispersed in the pigment dispersion is preferably 0.03 to 0.3 μm, which can be measured by a dynamic light scattering method.

[0666] Next, the pigment dispersion obtained by the dispersion treatment is mixed with other components contained in the photosensitive color resin composition to prepare a uniform solution or dispersion. In the production process of the photosensitive color resin composition, fine dust may be mixed into the liquid, so the obtained photosensitive color resin composition is preferably filtered using a filter or the like.

[0667] [cured material]

[0668] The cured product of the present invention can be obtained by curing the photosensitive color resin composition of the present invention. The cured product obtained by curing the photosensitive color resin composition of the present invention can be suitably used as a black matrix, an insulating film, or a partition wall, and can be more suitably used as a partition wall.

[0669] The film thickness of the cured product is preferably 0.5 μm or more, more preferably 0.7 μm or more, and further preferably 0.9 μm or more. In addition, it is preferably 15 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. For example, it is preferably 0.5 to 15 μm, more preferably 0.7 to 10 μm, and further preferably 0.9 to 5 μm.

[0670] Next, a cured product using the photosensitive coloring resin composition of the present invention will be described in terms of its production method.

[0671] (1) Support

[0672] As a support for forming a solidified product, as long as it has appropriate strength, its material is not particularly limited. Mainly used is a substrate, and as a material, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone and other thermoplastic resin films, epoxy resins, unsaturated polyester resins, poly (methyl) acrylic resins and other thermosetting resin sheets, various glasses. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred. In addition, sometimes a transparent electrode such as ITO, IZO or a metal electrode such as silver, gold, platinum, aluminum, and magnesium is formed on the surface of the substrate. In addition to the aforementioned substrate, it can also be formed on a TFT array.

[0673] In order to improve surface properties such as adhesiveness, the support may be subjected to, if necessary, a corona discharge treatment, an ozone treatment, or a film-forming treatment using a silane coupling agent or various resins such as a polyurethane resin.

[0674] The thickness of the support is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm. When thin film formation of various resins is performed, the film thickness is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[0675] On the support body where the cured product is to be provided, a photosensitive colored resin composition is applied in a film or pattern by a coating method or the like, and the solvent is dried. Then, patterning is performed by a method such as photolithography with exposure-development. Then, additional exposure and heat curing treatment are performed as needed to form a cured product on the substrate.

[0676] (2) Method of supplying to support

[0677] The photosensitive colored resin composition of the present invention is preferably supplied to the support in a state dissolved or dispersed in a solvent. As a supply method, it can be carried out by a conventionally known method, such as a spin coating method, a wire rod method, a flow coating method, a die coating method, a roller coating method, and a spray coating method. In addition, for example, it can also be supplied in a pattern by an inkjet method or a printing method. If a die coating method is used, it is preferred from a comprehensive point of view such as greatly reducing the amount of coating liquid used, completely eliminating the influence of mist attached when using a spin coating method, and suppressing the generation of foreign matter.

[0678] The coating amount varies depending on the application, and as a dry film thickness, it is preferably coated in a manner of 0.5 to 10 μm, more preferably 1 to 9 μm, and particularly preferably 1 to 7 μm. It is important that the dry film thickness or the height of the finally formed solidified product is uniform over the entire area of ​​the support. By reducing the deviation, the light-shielding property in the support becomes uniform, and in addition, when used as a partition, the light-emitting layer can be uniformly produced, which can suppress poor display during light emission.

[0679] When cured products having different heights are formed collectively by photolithography using the photosensitive color resin composition of the present invention, the heights of the cured products finally formed are different.

[0680] (3) Drying method

[0681] The drying after supplying the photosensitive color resin composition onto the support is preferably carried out by a drying method using a hot plate, an IR oven, or a convection oven. A reduced pressure drying method in which the composition is dried in a reduced pressure chamber without increasing the temperature may be combined.

[0682] The drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, etc. The drying time is preferably selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 130° C., and more preferably within the range of 30 seconds to 3 minutes at a temperature of 50 to 110° C., depending on the type of solvent component, the performance of the dryer used, etc.

[0683] (4) Exposure method

[0684] Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive color resin composition and irradiating a light source of ultraviolet light or visible light through the mask pattern. When exposure is performed using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive color resin composition, or a method of arranging the exposure mask at a position away from the coating film of the photosensitive color resin composition and projecting the exposure light through the exposure mask can be adopted. It can also be a scanning exposure method using a laser without using a mask pattern. If necessary, in order to prevent the sensitivity of the photopolymerizable layer from being reduced by oxygen, it can be performed in a deoxygenated atmosphere, or after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer, exposure can be performed.

[0685] When forming cured products of different heights at the same time by photolithography, for example, an exposure mask having a light shielding portion (transmittance 0%) and a plurality of openings having an average transmittance lower than that of the opening having the highest average transmittance (completely transmitting opening) (intermediately transmitting opening). According to this method, a difference in the residual film rate occurs due to the difference in average transmittance between the intermediately transmitting opening and the completely transmitting opening, that is, the difference in exposure amount.

[0686] The intermediate transmission opening is made by a matrix-shaped light shielding pattern having tiny polygonal light shielding units, for example. As the absorber, it is made by controlling the light transmittance of a film made of chromium, molybdenum, tungsten, or silicone materials, for example.

[0687] The light source used in the exposure is not particularly limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a fluorescent lamp and other lamp light sources, an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, a blue-violet semiconductor laser, a near-infrared semiconductor laser and other laser light sources can be cited. When using by irradiating light of a specific wavelength, an optical filter can also be utilized.

[0688] The optical filter may be a thin film type capable of controlling light transmittance at an exposure wavelength, and the material used in this case may include, for example, Cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), MoSi, Si, W, and Al.

[0689] The exposure dose is not particularly limited, but is preferably 1 mJ / cm 2 More preferably, 5 mJ / cm 2 More preferably, 10 mJ / cm 2 More than, preferably 300mJ / cm 2 Below, more preferably 200mJ / cm 2 Below, more preferably 150mJ / cm 2 the following.

[0690] (5) Development method

[0691] After the exposure, an image pattern can be formed on the support by development using an aqueous solution of a basic compound or an organic solvent. The aqueous solution of the basic compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

[0692] As the alkaline compound, for example, inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic alkaline compounds such as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline can be mentioned. These alkaline compounds can be used alone or in combination of two or more.

[0693] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglycerol alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0694] The surfactant may be used alone or in combination of two or more.

[0695] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. In addition, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.

[0696] The conditions for the development treatment are not particularly limited, but the development temperature is preferably 10 to 50° C., more preferably 15 to 45° C., and further preferably 20 to 40° C. The development method may be, for example, immersion development, spray development, brush development, or ultrasonic development.

[0697] (6) Additional exposure and heating curing treatment

[0698] The developed substrate can be exposed again as needed by the same method as the above exposure method. It is also possible to perform a heat curing treatment (also called calcining) after development or after additional exposure. The heat curing treatment conditions are: the temperature is preferably 100 to 280°C, more preferably 150 to 250°C, and the time is 5 to 60 minutes.

[0699] [next door]

[0700] The partition wall of the present invention is formed by the cured product of the present invention. That is, the photosensitive color resin composition of the present invention can be suitably used to form a partition wall, in particular, a partition wall for partitioning an organic layer of an organic electroluminescent element. In this case, the photosensitive color resin composition of the present invention itself becomes the partition wall.

[0701] Examples of the organic layer used in the organic electroluminescent element include an organic layer used in a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer described in Japanese Patent Application Laid-Open No. 2016-165396.

[0702] Specifically, the partition wall of the present invention is composed of the cured product of the present invention described above.

[0703] The partition wall is formed by applying the photosensitive coloring composition of the present invention in a film or pattern form to a support body where the partition wall is to be provided, and drying the solvent. Then, the pattern is formed by a method such as photolithography for exposure-development. Then, additional exposure and thermal curing treatment are performed as needed to form the partition wall on the support body. The specific methods of the supply method, drying method, exposure method, development method, additional exposure treatment and thermal curing treatment of the photosensitive coloring composition can include the various methods and treatment methods exemplified in the description of the cured product of the present invention mentioned above.

[0704] When the present invention is used as a partition wall, the size and shape can be appropriately adjusted according to the specifications of the organic electroluminescent element to which it is applied, and for example, the film thickness of the partition wall is preferably about 0.5 to 10 μm. The optical density (OD) per 1 μm film thickness of the partition wall formed from the photosensitive colored resin composition of the present invention is the same as that of the cured film.

[0705] The film thickness of the partition wall is measured by a step / surface roughness / fine shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, or an electron microscope.

[0706] [Organic electroluminescent element]

[0707] The organic electroluminescent element of the present invention includes a cured product, such as a partition wall, formed from the photosensitive color resin composition of the present invention.

[0708] For example, various organic electroluminescent elements are manufactured using a substrate with a partition wall pattern manufactured by the aforementioned method. The method for forming the organic electroluminescent element is not particularly limited, and preferably, after forming a partition wall pattern on a substrate by the aforementioned method, an organic layer such as a pixel is formed by a wet process such as a vapor deposition method, a casting method, a spin coating method, and an inkjet printing method in which a functional material is sublimated under a vacuum state and attached to the substrate in a region surrounded by the partition wall, thereby manufacturing the organic electroluminescent element.

[0709] Examples of the types of organic electroluminescent elements include bottom emission type and top emission type.

[0710] In the bottom emission type, for example, a partition wall is formed on a glass substrate laminated with a transparent electrode, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are laminated in the opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate laminated with a metal electrode layer as a reflective layer, and an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer are laminated in the opening surrounded by the partition wall.

[0711] Examples of the light-emitting layer include organic electroluminescent layers described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. In addition, quantum dots described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[0712] The layer structure is not limited thereto. For example, from the viewpoint of luminous efficiency, each of the hole transport layer and the electron transport layer may be a stacked structure consisting of two or more layers. The thickness of each layer is not particularly limited, but is preferably 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

[0713] The organic electroluminescent element can be separated into RGB colors according to each opening, or two or more colors can be stacked in one opening. From the viewpoint of improving reliability, the organic electroluminescent element can have a sealing layer. The sealing layer has the function of preventing moisture in the air from being adsorbed on the organic electroluminescent element and reducing the luminous efficiency. From the viewpoint of improving light extraction efficiency, the organic electroluminescent element can have a low-reflection film at the interface with the air. By configuring the low-reflection film at the interface between the air and the element, it can be expected to reduce the refractive index gap and suppress reflection at the interface. For example, the technology of moth-eye structure and super multi-layer film can be applied to such a low-reflection film.

[0714] When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from a light-emitting layer of a certain pixel from leaking to other pixels. Furthermore, when electrodes etc. are made of metal, it is necessary to prevent degradation of image quality due to reflection of external light. Therefore, it is preferred to impart light-shielding properties to the partition walls constituting the organic electroluminescent element.

[0715] In an organic electroluminescent element, electrodes need to be provided on the upper and lower surfaces of the partition wall, so from the viewpoint of insulation, the partition wall is preferably high-resistance and low-dielectric constant. Therefore, when a colorant is used to provide light-shielding properties to the partition wall, it is preferred to use the aforementioned organic pigment with high resistance and low dielectric constant.

[0716] [Color Filter]

[0717] The color filter of the present invention is not particularly limited as long as it includes the partition walls of the present invention, and examples thereof include color filters in which pixels are formed in regions partitioned by the partition walls. The color filter may also contain light-emitting nanoparticles.

[0718] Figure 1 Schematic cross-sectional view of an example of a color filter having a partition wall of the present invention. Figure 1 As shown, the color filter 100 includes a substrate 10, a partition wall 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50. The red pixel 30, the green pixel 40, and the blue pixel 50 are arranged in a grid shape in a repeated manner in this order. The partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are divided from each other by the partition wall 20.

[0719] The red pixel 30 includes red luminescent nanocrystal particles 2, and the green pixel 40 includes green luminescent nanocrystal particles 1. The blue pixel 50 is a pixel that transmits blue light from a light source.

[0720] These nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and have a maximum particle size of 100 nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope.

[0721] By absorbing light of a specified wavelength, luminescent nanocrystals can emit light of a wavelength different from the absorbed wavelength (fluorescence or phosphorescence). For example, red luminescent nanocrystals 2 emit light with a luminescence peak wavelength in the range of 605 to 665 nm (red light), and green luminescent nanocrystals 1 emit light with a luminescence peak wavelength in the range of 500 to 560 nm (green light).

[0722] According to the solution of the Schrödinger wave equation of the trap potential model, the wavelength (luminescent color) of the light emitted by the luminescent nanocrystal depends on the size (e.g., particle size) of the luminescent nanocrystal, but also depends on the energy gap possessed by the luminescent nanocrystal. Therefore, by changing the constituent material and size of the luminescent nanocrystal used, the luminescent color can be selected. As luminescent nanocrystals, quantum dots etc. can be cited.

[0723] The method for manufacturing the color filter containing the luminescent nanocrystal particles is not particularly limited, and the following method can be cited: preparing a substrate having a partition wall formed by the cured product of the present invention, and forming a layer containing the luminescent nanocrystal particles in the region divided by the partition wall. The method for forming the layer containing the luminescent nanocrystal particles is not particularly limited, and for example, the method can be manufactured by the following method: selectively attaching an ink composition containing the luminescent nanocrystal particles by inkjet method, and curing the ink composition by irradiation with active energy rays or heating.

[0724] [Image display device]

[0725] The image display device of the present invention includes an organic EL display device having a partition wall composed of the cured product of the present invention and an organic electroluminescent element. That is, the image display device of the present invention includes the partition wall of the present invention.

[0726] As long as the organic EL display device includes the aforementioned organic electroluminescent element, there is no particular restriction on the model and structure of the image display device. For example, an active drive type organic electroluminescent element can be used for assembly according to a conventional method. For example, it can be formed by the method described in "Organic EL Display" (Ohm Company, published on August 20, 2001, by Shizuo Tokito, Chiba Ya Andachi, and Hideyuki Murata). For example, an organic electroluminescent element emitting white light and a color filter can be combined to display an image, or organic electroluminescent elements with different luminous colors such as RGB can be combined to display an image.

[0727] Example

[0728] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist of the present invention.

[0729] The constituent components of the photosensitive coloring resin composition used in the following Examples and Comparative Examples and their evaluation methods are as follows.

[0730] <Alkali Soluble Resin-I>

[0731] [Chemistry 43]

[0732]

[0733] 100 parts by mass of an epoxy compound having a repeating unit represented by the above formula (epoxy equivalent 273), 26.42 parts by mass of acrylic acid, 2.53 parts by mass of triphenylphosphine and 84.28 parts by mass of propylene glycol monomethyl ether acetate were placed in a reaction container and stirred. Then, 6.84 parts by mass of trimellitic anhydride and 48.98 parts by mass of propylene glycol monomethyl ether acetate were further added and reacted.

[0734] The alkali-soluble resin-I thus obtained had a weight average molecular weight Mw of 2500 and an acid value of 27.2 mgKOH / g as measured by GPC.

[0735] It does not belong to the polyamideimide (meth)acrylate resin (C-1).

[0736] <Alkali Soluble Resin-II>

[0737] A polyamideimide (meth)acrylate resin obtained from a reaction product of a polyamideimide resin having a terminal acid group or anhydride group obtained by reaction of an isocyanurate type polyisocyanate with tricarboxylic anhydride and a (meth)acrylate having an epoxy group in the molecule and tricarboxylic anhydride.

[0738] The weight average molecular weight is 5100 and the acid value is 80 mgKOH / g.

[0739] This corresponds to the polyamideimide (meth)acrylate resin (C-1).

[0740] Specifically, the following compounds are given.

[0741] Isocyanurate polyisocyanate: 242.8 g of an isocyanurate-modified product of isophorone diisocyanate ("VESTANATT-1890 / 100" manufactured by Evonik Corporation, isocyanate group content 17.3% by mass) (corresponding to compound (C-1-11).)

[0742] Tricarboxylic acid anhydride: 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (corresponding to compound (C-1-12))

[0743] (Meth)acrylate having an epoxy group in the molecule: 170.4 g of glycidyl methacrylate (corresponding to compound (C-1-2))

[0744] Tricarboxylic acid anhydride: 118.8 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (corresponding to compound (C-1-13))

[0745] Alkali-soluble resin-II can be produced by the method described in Japanese Patent Application Laid-Open No. 2023-55623.

[0746] <Alkali-soluble resin-III>

[0747] "KBR-201" manufactured by KISCO Corporation. A resin having a bisphenol fluorene skeleton.

[0748] Weight average molecular weight: 5107, acid value: 113 mgKOH / g.

[0749] This corresponds to the epoxy (meth)acrylate resin (C-2) having an aromatic ring in the main chain.

[0750] <Alkali-soluble resin-IV>

[0751] A commercially available aliphatic carboxylic acid-containing polyamide-imide resin, trade name EMG-1015 (manufactured by DIC Corporation) was prepared.

[0752] Acid value: 155mgKOH / g.

[0753] It does not contain an acryloyl group and does not belong to the polyamide-imide (meth)acrylate resin (C-1).

[0754] <Alkali Soluble Resin-V>

[0755] [Chemistry 44]

[0756]

[0757] 50.0 parts by mass of the epoxy compound of the chemical structure represented by the above formula, 170.3 parts by mass of propylene glycol monomethyl ether acetate, 0.89 parts by mass of 2,4,6-trisdimethylaminomethylphenol, and 0.050 parts by mass of p-methoxyphenol were stirred while nitrogen substitution was performed, and the temperature was raised to 100° C. 44.3 parts by mass of methacrylic acid was added dropwise thereto over 30 minutes. The mixture was further reacted at 100° C. for 8 hours until the acid value became 10 mgKOH / g or less, and epoxy methacrylate solution A was obtained.

[0758] [Chemistry 45]

[0759]

[0760] 50.0 parts by mass of epoxy methacrylate solution A (solid content concentration: 35.9% by mass) of the epoxy methacrylate compound having the above chemical structure and 3.1 parts by mass of propylene glycol monomethyl ether acetate were stirred while nitrogen substitution was performed, 3.48 parts by mass of pyromellitic dianhydride (PDMA) and 2.36 parts by mass of phthalic anhydride were added, the temperature was raised to 80°C, and the reaction was carried out for 5 hours.

[0761] The alkali-soluble resin-V had a solid content of 40% by mass, an acid value of 145 mgKOH / g, and a polystyrene-equivalent weight average molecular weight (Mw) of 2,800 as measured by GPC.

[0762] It does not belong to the polyamideimide (meth)acrylate resin (C-1).

[0763] <Colorant-I>

[0764] Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation) (having a chemical structure represented by the following formula (A-1-2)).

[0765] [Chemistry 46]

[0766]

[0767] <Dispersant-I>

[0768] A block copolymer comprises an A block containing a repeating unit having a solvent-philic group and a B block containing a repeating unit having a tertiary amino group and a quaternary ammonium group.

[0769] <Solvent-I>

[0770] PGMEA: Propylene glycol monomethyl ether acetate

[0771] <Solvent-II>

[0772] MB: 3-methoxy-1-butanol

[0773] <Photopolymerization Initiator-I>

[0774] Oxime ester-based photopolymerization initiator having the following chemical structure.

[0775] [Chemistry 47]

[0776]

[0777] <Ethylenically Unsaturated Compounds-I>

[0778] DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

[0779] <Surfactant-I>

[0780] DIC Megafac F-559

[0781] <Measurement of Optical Density per Unit Film Thickness (Unit OD Value)>

[0782] The optical density per unit film thickness was measured by the following procedure.

[0783] The photosensitive colored resin composition of each example and comparative example was applied onto a glass substrate using a spin coater to a thickness of 1.5 μm after heat curing (baking), and then dried in a vacuum dryer for 60 seconds, followed by heating and drying on a hot plate heated to 100° C. for 100 seconds.

[0784] The obtained coating film was exposed without using an exposure mask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used as an irradiation light source, and the exposure amount was 80 mJ / cm 2 The exposure was performed for 20 seconds. The illumination was 500mW / cm 2 Next, the resist-coated substrate 1 was obtained by heat-curing in an oven at 230° C. for 30 minutes.

[0785] The optical density (OD value) of the resist-coated substrate 1 obtained was measured using a 361T(V) transmission densitometer manufactured by X-Rite (color temperature of the illumination light source: about 2850K (equivalent to CIE standard light source A), spectral sensitivity characteristics of the light receiving part: ISO visual density in ISO 5-3 standard), and the film thickness was measured using VertScan(R)2.0, a non-contact surface / layer cross-sectional shape measurement system manufactured by Ryoka Systems, Inc. The optical density (unit OD value) per unit film thickness (1 μm) was calculated from the optical density (OD value) and the film thickness. In addition, the OD value is a numerical value indicating the light-shielding ability, and a larger numerical value indicates a higher light-shielding property.

[0786] <Preparation of Smoke Amount Measurement Substrate>

[0787] Measure the weight W1 (mg) of a glass substrate of 5cm×5cm size. Use a spin coater to apply the photosensitive colored resin composition of each embodiment and comparative example on the glass substrate in a manner such that the thickness becomes 1.5μm after heat curing treatment (firing). Then, dry it in a vacuum dryer for 60 seconds. Next, heat and dry it on a hot plate heated to 100°C for 100 seconds to obtain a coated substrate. Next, expose the obtained coating without using an exposure mask. As the irradiation light source, use an intensity of 40mW / cm at a wavelength of 365nm. 2 The exposure was set to 40 mJ / cm 2 The weight W2 (mg) of the substrate after exposure was measured. The substrate after exposure was fired in an oven at 230° C. for 30 minutes to obtain a fume amount measurement substrate. The weight W3 (mg) of the substrate after firing was measured.

[0788] <Evaluation of smoke volume>

[0789] The amount of smoke during burning is calculated using the following formula.

[0790] Smoke volume (%) = {(substrate weight after exposure W2 - substrate weight after firing W3) / (substrate weight after exposure W2 - glass substrate weight W1)} × 100 (%)

[0791] The amount of smoke is determined as follows.

[0792] A: Smoke volume less than 10%

[0793] B: Smoke volume is greater than 10% and less than 12%

[0794] C: Smoke volume more than 12%

[0795] It should be noted that the smaller the amount of smoke, the better, with A being the best, and if it is 12% or less, there tends to be no problem in practical use.

[0796] <Preparation of Substrate for Evaluation of Residual Film Rate>

[0797] On a substrate (ITO substrate) having an indium tin oxide (ITO) film formed on the surface of a glass substrate having a film thickness of 0.7 mm, the photosensitive colored resin composition of each example and comparative example was applied using a spin coater so that the thickness became 1.5 μm after heat curing treatment (baking). Then, a drying treatment was performed for 60 seconds in a vacuum dryer. Next, the coating was dried for 100 seconds on a hot plate heated to 100° C. to obtain a coated substrate.

[0798] The film thickness of the coating film of the coating film substrate was measured by the method described later to determine the film thickness T1 (μm).

[0799] The obtained coating film substrate was exposed using a photomask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used at an exposure dose of 80 mJ / cm 2 The exposure was performed for 20 seconds. The illumination was 500mW / cm 2 The slit width was 1.6 mm. A mask having a grid-shaped opening (having a 50 μm square-shaped covering portion and a plurality of the above-mentioned covering portions separated by a 50 μm wide grid-shaped exposure portion) was used as the photomask.

[0800] Next, a developer consisting 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 after spray development at a water pressure of 0.05 MPa was performed at 24°C, the developer was flowed with pure water, the development was stopped, and the film was washed with a water washing sprayer for 10 seconds. The spray development time was set to 1.6 times the time for the unexposed part of the coating film to be dissolved and removed. The portion corresponding to the square light shielding portion flows through the photosensitive coloring resin composition after development, so the ITO substrate is exposed to form a hole portion.

[0801] The substrate was baked in an oven at 230° C. for 30 minutes to obtain a pattern substrate for patterning property measurement. The film thickness T2 (μm) of the coating film at this time was measured.

[0802] <Calculation of residual film rate>

[0803] The film thickness of the coating film in each process (after drying and after firing) in the production of the aforementioned pattern substrate was measured using the non-contact surface / layer cross-sectional shape measurement system VertScan(R)2.0 manufactured by Ryoka Systems Co., Ltd. In measuring the film thickness, the ratio of the film thickness (T2) of the coating film in the pattern substrate to the film thickness (T1) of the coating film in the coating substrate was calculated as the residual film rate.

[0804] Residual film rate (%) = T2 / T1×100 (%)

[0805] <Evaluation of residual film rate>

[0806] The calculated residual film ratio was judged as follows: A means the residual film ratio is the highest and is good, and if the residual film ratio is 75% or more, there is a tendency that there is no problem in practical use.

[0807] A: Residual film rate is more than 75%

[0808] B: The residual film rate is less than 75% and more than 60%

[0809] C: Residual film rate is less than 60%

[0810] It should be noted that the residual film rate is related to the exposure sensitivity of the photosensitive color resin composition, the solubility in the developer, and the thermal decomposition during firing, and the higher the residual film rate, the better.

[0811] Evaluation method of luminescence characteristics

[0812] <Production of Patterned Substrate for Organic Electroluminescent Element>

[0813] A 70 nm thick indium tin oxide (ITO) transparent conductive film was deposited on glass, and the substrate with the anode formed thereon was coated with the photosensitive colored resin composition of each embodiment and comparative example using a spin coater using conventional photolithography and hydrochloric acid etching, so that the thickness was 1.5 μm after heat curing (baking). Then, a vacuum dryer was used for 60 seconds to dry the film. Next, the film was heated and dried on a hot plate heated to 100°C for 100 seconds.

[0814] The obtained coating film substrate was exposed using a photomask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used at an exposure dose of 80 mJ / cm 2 The exposure was performed for 20 seconds. The illumination was 500mW / cm 2 The slit width was 1.6 mm. A mask having a lattice-shaped opening (having a rectangular covering portion of 40 μm in length and 80 μm in width, with a plurality of the covering portions spaced 20 μm apart in the major and minor axis directions) was used.

[0815] Next, a developer solution consisting of an aqueous solution containing 0.05 mass % of potassium hydroxide and 0.08 mass % of a nonionic surfactant ("A-60" manufactured by Kao Corporation) was used to perform shower development at a water pressure of 0.05 MPa at 24° C., and then the developer solution was flowed with pure water to stop the development and wash with a water washing sprayer for 10 seconds. The shower development time was set to 1.6 times the time it took for the unexposed portion of the coating film to be dissolved and removed.

[0816] Through these operations, the openings were developed and removed to obtain an electrode substrate with patterned partition walls. The electrode substrate with the pattern was heated and cured (baked) in an oven at 230° C. for 30 minutes to obtain a patterned substrate for an organic electroluminescent element.

[0817] <Fabrication of Device for Evaluation of Organic Electroluminescent Element>

[0818] On the entire surface of the pattern substrate for the prepared organic electroluminescent element, molybdenum oxide with a film thickness of 10 nm as a hole injection layer, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-9H-fluorene-2-amine with a film thickness of 60 nm as a hole transport layer, tri(8-hydroxyquinoline)aluminum with a film thickness of 60 nm as a light-emitting layer, 8-hydroxyquinoline-lithium with a film thickness of 1 nm as an electron injection layer, and aluminum with a film thickness of 80 nm as a cathode are sequentially stacked by vacuum evaporation to produce an organic electroluminescent element.

[0819] Next, a desiccant is attached to the concave portion of the sealing glass having a concave portion at the center, and a UV curing resin is applied to the frame portion around the concave portion. The sealing glass is arranged so that the concave portion of the sealing glass completely covers the organic electroluminescent element on the aforementioned electrode substrate, and the sealing glass is attached to the aforementioned electrode substrate, and the UV curing resin is irradiated with UV to cure it, thereby sealing the hollow structure, thereby manufacturing a device for evaluating the organic electroluminescent element.

[0820] <Evaluation of Light Emitting Characteristics of Organic Electroluminescent Element>

[0821] A direct current was passed through the produced device for evaluating the organic electroluminescent element, and the current density at a driving voltage of 6 V was measured.

[0822] The current density is determined as follows: The higher the current density, the better. If the current density is 6 mA / cm 2 The above tends to be practically problem-free.

[0823] A: Current density 6mA / cm 2 above

[0824] B: Current density is less than 6mA / cm 2

[0825] <Preparation of Pigment Dispersion Liquid-1>

[0826] The pigment, dispersant, alkali-soluble resin and solvent listed in Table 1 were mixed in the mass ratio listed in Table 1. The mixed solution was dispersed in a paint shaker at 25 to 45° C. for 3 hours. Zirconia beads of 2.5 times the mass of the dispersion were added. After the dispersion was completed, the beads were separated from the dispersion using a filter to prepare pigment dispersion-1.

[0827] It should be noted that the amount of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[0828] [Table 1]

[0829]

[0830] [Examples 1 to 9, Reference Examples 1 to 4, Comparative Examples 1 to 6]

[0831] A mixed solvent of PGMEA (propylene glycol monomethyl ether acetate) / MB (3-methoxybutanol) = 80 / 20 was added as a solvent so that the content ratio of the solid content of each component in the total solid content became the value described in Table 2, and the content ratio of the total solid content became 17% by mass, and the mixture was stirred and dissolved to prepare a photosensitive color resin composition.

[0832] Table 2 shows the evaluation results of the optical density per unit film thickness, the amount of haze, and the residual film rate, and the evaluation results of the light-emitting characteristics of the organic electroluminescent element.

[0833] [Table 2]

[0834]

[0835] The results of Reference Examples 1 to 4 and Comparative Example 1 show that the amount of smoke generated during firing is reduced by using the polyamideimide (meth)acrylate resin (C-1). This is believed to be because the polyamideimide (meth)acrylate resin (C-1) has an isocyanurate skeleton and amide bonds and imide bonds, and thus has a strong intermolecular force and tends to be less likely to be thermally decomposed during heat treatment.

[0836] From the results of Reference Example 1 and Comparative Example 1, it can be seen that the residual film rate of the photosensitive colored resin composition containing a colorant is also high by using the polyamideimide (meth) acrylate resin (C-1). It is believed that the polyamideimide (meth) acrylate resin (C-1) has a (meth) acryloyl group, and even if it contains a colorant, it can form a strong cured film after exposure, and the residual film rate after firing can be maintained at a high level.

[0837] As can be seen from Examples 1 to 3, the residual film rate is further improved by using the polyamide-imide (meth)acrylate resin (C-1) and the epoxy (meth)acrylate resin (C-2) having an aromatic ring in the main chain. This is considered to be because the epoxy (meth)acrylate resin (C-2) having an aromatic ring in the main chain has high developer resistance during development and high heat resistance at the firing temperature because it contains an aromatic ring in the main chain.

[0838] Examples 1 to 9 tend to have high current density during light emission. This is presumably because the polyamide-imide (meth)acrylate resin (C-1) has an isocyanurate skeleton and amide bonds and imide bonds, which results in strong intermolecular forces and a tendency to be difficult to thermally decompose during heat treatment, and a small amount of smoke is generated during firing, and a small amount of decomposition products are accumulated in the pixel portion of the organic electroluminescent element, so that current flows easily when the same voltage is applied.

[0839] In Comparative Examples 4 and 5, the pigment content is low, the optical density per 1 μm film thickness of the cured coating is low, and the current density during light emission is high. This is believed to be due to the high transmittance of ultraviolet rays in the coating, the increased photocurability, the difficulty in thermal decomposition during heat treatment, and the reduced accumulation of decomposed products in the pixel portion of the organic electroluminescent element, and is not presumed to be due to the difference in (C) the alkali-soluble resin.

[0840] In Comparative Examples 2 and 6, the pigment content is sufficiently high, the optical density per 1 μm film thickness of the cured coating is high, and the current density is low. The reason is presumed to be that if a colorant is included in the composition to ensure light-shielding properties, the photopolymerizable component is reduced and light is shielded, so that the photocuring inside the film becomes insufficient, and the unreacted low-molecular components are easily thermally decomposed during the heat treatment, so that the accumulation of decomposition products in the pixel portion of the organic electroluminescent element increases.

[0841] In contrast, Examples 1 to 9 contain the polyamideimide (meth)acrylate resin (C-1), and therefore it is estimated that the accumulation of decomposition products in the pixel portion of the organic electroluminescent element is small, and the current density during light emission is high.

[0842] Description of Reference Numerals

[0843] 1. Green luminescent nanocrystals

[0844] 2Red luminescent nanocrystals

[0845] 10 substrates

[0846] 20 Next Door

[0847] 30 red pixels

[0848] 40 green pixels

[0849] 50 blue pixels

[0850] 100 color filters.

Claims

1. A photosensitive colored resin composition comprising (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated compound, The (C) alkali-soluble resin contains a polyamideimide (meth)acrylate resin (C-1), The polyamideimide (meth)acrylate resin (C-1) is a resin obtained by reacting a compound (C-1-2), a compound (C-1-3) and a polyamideimide resin (C-1-1). The polyamide-imide resin (C-1-1) is a polyamide-imide resin having a terminal acid group or anhydride group obtained by reacting a compound (C-1-11) with a compound (C-1-12). The compound (C-1-11) is an isocyanurate type polyisocyanate, The compound (C-1-12) is a tricarboxylic anhydride, The compound (C-1-2) is a (meth)acrylate having an epoxy group in the molecule. The compound (C-1-3) is a dicarboxylic anhydride and / or a tricarboxylic anhydride, The (C) alkali-soluble resin further contains an alkali-soluble resin other than the polyamideimide (meth)acrylate resin (C-1), The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more.

2. The photosensitive colored resin composition according to claim 1, wherein The (A) colorant contains an organic pigment.

3. The photosensitive colored resin composition according to claim 2, wherein The organic pigment contains an organic black pigment.

4. The photosensitive colored resin composition according to claim 3, wherein The organic black pigment contains a benzodifuranone-based organic black pigment.

5. The photosensitive colored resin composition according to claim 4, wherein The benzodifuranone-based organic black pigment contains the following organic black pigment: comprising at least one selected from the group consisting of a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, and a salt of a geometric isomer thereof, [Chemistry 1] In formula (A-1-1), R 611 and R 616 Each independently represents a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom; R 612 , R 613 , R 614 , R 615 , R 617 , R 618 , R 619 and R 620 Each independently represents a hydrogen atom, a halogen atom, R 621 、COOH、COOR 621 、COO - ,CONH2,CONHR 611 ,CONR 621 R 622 、CN、OH、OR 621 、COCR 621 、OOCNH2、OOCNHR 621 、OOCNR 621 R 622 、NO2、NH2、NHR 621 NR 621 R 622 、NHCOR 622 NR 621 COR 622 、N=CH2、N=CHR 621 、N=CR 621 R 622 , SH, SR 621 , SOR 621 、SO2R 621 、SO3R 621 、SO3H、SO3 - 、SO2NH2、SO2NHR 621 or SO2NR 621 R 622 ; Select from R 612 and R 613 , R 613 and R 614 , R 614 and R 615 , R 617 and R 618 , R 618 and R 619 and R 619 and R 620 At least one of the groups may be directly bonded to each other, or may be bonded to each other through an oxygen atom, a sulfur atom, NH or NR 621 Bridge and bond to each other; R 621 and R 622 Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

6. The photosensitive colored resin composition according to claim 1, wherein The content of the (A) colorant is 10% by mass or more relative to the total solid content of the photosensitive color resin composition.

7. The photosensitive colored resin composition according to claim 1, wherein The (C) alkali-soluble resin contains an epoxy (meth)acrylate resin (C-2) having an aromatic ring in its main chain as the alkali-soluble resin other than the polyamideimide (meth)acrylate resin (C-1).

8. The photosensitive colored resin composition according to claim 1, wherein The content ratio of the polyamideimide (meth)acrylate resin (C-1) in the (C) alkali-soluble resin is 10% by mass or more and 90% by mass or less.

9. The photosensitive colored resin composition according to claim 1, wherein The content ratio of the (C) alkali-soluble resin is 100 parts by mass or more relative to 100 parts by mass of the (E) ethylenically unsaturated compound. 10 . The photosensitive colored resin composition according to claim 1 , which is used for forming a partition wall. 11 . A cured product obtained by curing the photosensitive color resin composition according to claim 1 . 12 . A partition wall formed of the cured product according to claim 11 . 13 . An organic electroluminescent element comprising the partition wall according to claim 12 . 14 . A color filter comprising the partition wall according to claim 12 and light-emitting nanocrystal particles. 15 . An image display device comprising the partition wall according to claim 12 .

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