Photosensitive Composition, Optical Filter, Image Display Device, and Solid-State Image Sensor

Abstract

To provide a photosensitive composition which is excellent in storage stability, enables formation of a pattern which has little development residues and has excellent shape and resistance, and has less foreign substances.SOLUTION: A photosensitive composition is provided, including a pigment (A), a dispersion resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a binder resin (E). The photopolymerization initiator (D) includes a compound (D1) represented by the following formula, and a photopolymerization initiator (D2) other than the compound (D1) and represented by the following formula, and does not substantially include an oxime compound. In the formula, R1 and R2 each independently represent a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive composition and its use.

Background Art

[0002] A color filter, which is a type of optical filter used in image display devices, solid-state imaging devices, etc., has two or more fine strip-shaped filter segments with different hues arranged parallel to each other (in a stripe pattern) or intersecting on a transparent substrate such as a glass substrate. Alternatively, two or more fine filter segments with different hues are arranged so as to be sequentially arranged in each of the vertical and horizontal directions. These filter segments have small dimensions of several microns to several hundred microns and are neatly arranged in a predetermined arrangement for each hue.

[0003] Currently, the manufacturing method of a color filter includes a step of applying a photosensitive composition to a transparent substrate such as glass and removing the solvent from this coating film by drying, a step of irradiating and curing (hereinafter referred to as exposure) this coating film with radiation through a photomask having a desired pattern shape, then a step of washing and removing the unexposed portion of this coating film (hereinafter referred to as development), and then a step of heat treatment (hereinafter referred to as post-baking) to sufficiently cure the cured film as necessary to obtain a filter segment pattern of the first color. Then, by performing the same operation, filter segment patterns of other colors are formed to complete the color filter.

[0004] The photosensitive composition is usually used after being stored for several weeks to several months after production. In that case, there has been a problem that the viscosity and sensitivity of the photosensitive composition change depending on the storage period.

[0005] If there are variations in the sensitivity of the photosensitive composition, when manufacturing a color filter under the same conditions, variations occur in developability, pattern shape, etc. In that case, it is necessary to change the manufacturing conditions of the color filter according to the photosensitive composition used, resulting in a decrease in productivity. Therefore, a photosensitive composition with excellent stability over time is required.

[0006] Furthermore, in recent years, color filters are required to have increasingly high transmittance and high color purity, and a photosensitive composition capable of producing a color filter with few foreign matters is demanded.

[0007] In addition, due to the miniaturization and high pixel density of image display devices and solid-state imaging devices, the area per pixel tends to become smaller, and color filters are required to be made thinner. And even if the color filter is made thinner, its spectral characteristics need to be maintained at the conventional level. Then, it is necessary to increase the concentration of the pigment contained in the pixels of the color filter, which relatively reduces the components required for curing, resulting in problems such as deterioration of developability, pattern shape, and resistance.

[0008] To solve the above problems, various efforts have been made. For example, Patent Document 1 discloses a radiosensitive resin composition excellent in the temporal stability of sensitivity, which contains an oxime ester compound having at least one kind of group selected from a branched alkyl group and a cyclic alkyl group, and the water content is 0.1 to 2% by mass based on the mass of the radiosensitive resin composition. Patent Document 2 discloses a radiosensitive composition for forming a green pixel containing a compound with a specific structure and an O-acyl oxime-based compound. Patent Document 3 discloses a resin composition containing a compound having a fluorocarbon group and a crosslinked alicyclic aliphatic group. Patent Document 4 discloses a fluorene-based polyfunctional photoinitiator with a specific structure having excellent solubility.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] However, none of the compositions described in Patent Documents 1 to 4 could satisfy all of storage stability (viscosity, sensitivity), suppression of foreign matter, developability, and pattern shape and resistance at a certain level or higher.

[0011] An object of the present invention is to provide a photosensitive composition that is excellent in storage stability, has few development residues, has excellent shape and resistance, and can form a pattern with few foreign matters.

MEANS FOR SOLVING THE PROBLEMS

[0012] The present invention is a photosensitive composition containing a pigment (A), a dispersion resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a binder resin (E), wherein the photopolymerization initiator (D) includes a compound (D1) represented by the following general formula (1) and a photopolymerization initiator (D2) other than the compound (D1) represented by the following general formula (1), and the photopolymerization initiator (D) relates to a photosensitive composition that substantially does not contain an oxime compound.

[0013]

CHEMICAL FORMULA

[0014] (In the general formula (1), R 1 , R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R 3 represents a hydrogen atom or a monovalent substituent.)

EFFECTS OF THE INVENTION

[0015] According to the present invention described above, it is possible to provide a photosensitive composition that is excellent in storage stability, has few development residues, has excellent shape and resistance, and can form a pattern with few foreign matters. Further, the present invention can provide an optical filter, an image display device, and a solid-state imaging device.

Embodiments for Carrying Out the Invention

[0016] Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0017] In the present invention, “(meth)acryloyl”, “(meth)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” means “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively, unless otherwise specified. Further, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compound in the present invention, for a low-molecular compound whose molecular weight can be specified, it is the value calculated by calculation (formula weight) or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and for a compound having a molecular weight distribution, it is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent. A monomer is a compound that forms a resin by polymerization. A monomer is an unreacted compound, and a monomer unit is a partial structure in which the monomer forms a resin after polymerization.

[0018] Although the mechanism by which the problems of the present invention can be solved with the photosensitive composition having the above configuration is not clear, it is presumed as follows.

[0019] Compared with the oxime compounds that have been widely used in the field of color filters, it is speculated that the compound (D1) represented by the general formula (1) has low sensitivity and is difficult to be activated by impurities (such as moisture and metal ions) contained in the photosensitive composition during storage, resulting in improved storage stability. Also, compared with acetophenone compounds with low sensitivity such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, it is speculated that the compound (D1) represented by the general formula (1) has a rigid and highly crystalline fluorene skeleton, so a cured film with high resistance can be obtained. Moreover, due to the π-π interaction between the two benzene rings, the cured film has high cohesive force. Therefore, it is speculated that pattern chipping in the development process is suppressed. On the other hand, since the compound (D1) represented by the general formula (1) has high crystallinity, the developability decreases and foreign matters are likely to occur. However, it is speculated that by using in combination a photoinitiator (D2) having a structure different from that of the compound (D1) represented by the general formula (1), the cohesive force is relaxed, the developability is improved, and an excellent pattern with few foreign matters can be obtained.

[0020] <Photosensitive composition> One embodiment of the present invention relates to a photosensitive composition. The photosensitive composition of the present invention is a photosensitive composition containing a pigment (A), a dispersion resin (B), a polymerizable compound (C), a photoinitiator (D), and a binder resin (E), wherein the photoinitiator (D) includes a compound (D1) represented by the following general formula (1) and a photoinitiator (D2) other than the compound (D1) represented by the following general formula (1), and the photoinitiator (D) is substantially free of oxime compounds.

[0021] General formula (1) [Chemical formula]

[0022] (In general formula (1), R 1 , R 2Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R 3 represents a hydrogen atom or a monovalent substituent. )

[0023] Hereinafter, the components contained or that can be contained in the photosensitive composition of one embodiment will be described in detail.

[0024] [Photopolymerization initiator (D)] The photosensitive composition of the present invention contains, as the photopolymerization initiator (D), a compound (D1) represented by the general formula (1) and a photopolymerization initiator (D2) other than the compound (D1) represented by the following general formula (1), and substantially does not contain an oxime compound.

[0025] (Compound (D1) represented by general formula (1)) The photosensitive composition of the present invention contains, as the photopolymerization initiator (D), a compound (D1) represented by the general formula (1).

[0026] General formula (1) [Chemical formula]

[0027] (In general formula (1), R 1 , R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R 3 represents a hydrogen atom or a monovalent substituent. )

[0028] R 1 , R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, cyclic, or a combination thereof. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. Among them, from the perspective of the pattern shape, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0029] R 3 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include an alkyl group having 1 to 20 carbon atoms such as methyl group and ethyl group; an alkoxy group having 1 to 20 carbon atoms such as methoxy group and ethoxy group; a halogen atom such as F, Cl, Br, and I; an acyl group having 1 to 20 carbon atoms; an alkyl ester group having 1 to 20 carbon atoms; an alkoxycarbonyl group having 1 to 20 carbon atoms; a halogenated alkyl group having 1 to 20 carbon atoms, an aromatic ring group having 4 to 20 carbon atoms; an amino group; an aminoalkyl group having 1 to 20 carbon atoms; a hydroxyl group; a nitro group; a cyano group; a benzoyl group which may have a substituent; a tenoyl group which may have a substituent, etc. Examples of the substituent that the benzoyl group or tenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, etc. Among them, from the perspective of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0030] Examples of the method for producing the compound (D1) represented by the general formula (1) include the methods described in Japanese Patent Application Laid-Open No. 2019-507108, Japanese Patent Application Laid-Open No. 2019-528331, etc.

[0031] Hereinafter, specific examples of the compound (D1) represented by the general formula (1) are shown. However, the present invention is not limited thereto.

[0032] Chemical formula (2)

Chem.

[0033] Chemical formula (3)

Chem.

[0034] Chemical formula (4)

Chem.

[0035] Among the compounds of chemical formulas (2) to (4), from the viewpoints of pattern shape and resistance, the compound of chemical formula (2) is preferred.

[0036] The compound (D1) represented by the general formula (1) can be used alone or in combination of two or more.

[0037] (Photoinitiator (D2) other than the compound (D1) represented by the general formula (1)) The photosensitive composition of the present invention contains a photoinitiator (D2) other than the compound (D1) represented by the general formula (1) as the photoinitiator (D).

[0038] Examples of the photoinitiator (D2) include alkylphenone compounds such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Biimidazole compounds such as 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds; titanocene compounds and the like. Among these, from the viewpoint of the pattern shape, it is preferably contains at least one selected from the group consisting of an alkylphenone compound, an acylphosphine oxide compound, and a biimidazole compound, and more preferably contains an alkylphenone compound.

[0039] Among the alkylphenone compounds, it is preferably contains at least one selected from 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and more preferably contains 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone from the viewpoint of stability over time.

[0040] The photopolymerization initiator (D2) can be used alone or in combination of two or more.

[0041] The mass ratio of the compound (D1) represented by the general formula (1) to the photopolymerization initiator (D2) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70 from the viewpoints of developability, pattern shape, resistance, and suppression of foreign matters.

[0042] The photopolymerization initiator (D) substantially does not contain an oxime compound. Here, substantially not containing means that it is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably 0.01% by mass or less in 100% by mass of the photopolymerization initiator (D).

[0043] By not containing an oxime compound, deterioration of storage stability and generation of foreign matters can be suppressed.

[0044] From the viewpoint of photocurability, the content of the photopolymerization initiator (D) is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound (C).

[0045] [Pigment (A)] The photosensitive composition of the present invention contains a pigment (A).

[0046] The pigment (A) is not particularly limited and may be either an organic pigment or an inorganic pigment, and they can also be used in combination.

[0047] (Organic pigment) Examples of organic pigments include C.I. 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, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A No. 2014-134712, the pigments described in Patent No. 6368844, etc.; C.I. Pigment Orange 36, 38, 43, 63, 64, 71, 73, etc.; C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments and the like described in JP-A-2012-226110; C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc.; C.I. 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, 79, etc.; C.I. 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, 50, etc.; Examples include C.I. Pigment Black 31 and the like. The organic pigments can be used alone or in combination of two or more.

[0048] (Inorganic Pigment) Examples of the inorganic pigment include carbon black, titanium black, silica, zinc white, lead white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, iron oxide red, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, dark blue, chromium oxide green, cobalt green, amber, synthetic iron black, alumina, zirconium oxide, calcium carbonate, barium titanate, aluminum oxide, magnesium oxide, zinc oxide, etc. The inorganic pigment can be used alone or in combination of two or more kinds.

[0049] The content of the pigment (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0050] (Subdivision of the pigment (A)) The pigment (A) is preferably used after being subdivided. The subdivision method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used. Among these, salt milling treatment by a kneader method which is a kind of wet grinding is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the subdivided pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0051] The salt milling treatment is a treatment in which a mixture of the pigment (A), a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while heating using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, etc., and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment (A) is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions when the pigment (A) is subjected to salt milling treatment, a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution can be obtained.

[0052] Examples of the water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. From the perspective of price, sodium chloride (table salt) is preferred. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment (A), from the viewpoints of both treatment efficiency and production efficiency.

[0053] The water-soluble organic solvent functions to wet the pigment (A) and the water-soluble inorganic salt, and is a solvent that dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, from the viewpoint of safety, a high-boiling solvent with a boiling point of 120 °C or higher is preferred. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment (A).

[0054] For the salt milling treatment, a resin may be added as necessary. The type of the resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in the above organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass, based on 100 parts by mass of the pigment (A).

[0055] [Dispersion resin (B)] The photosensitive composition of the present invention contains a dispersion resin (B). The dispersing resin (B) has a pigment-affinity site that has the property of adsorbing to the pigment (A) and a site that is compatible with the binder resin (E), and it suffices that it functions to adsorb to the pigment (A) and stabilize the dispersion in the binder resin (E). As is well known, the dispersing resin (B) is used in the production of a dispersion of the pigment (A), which is a precursor of the photosensitive composition, and is distinguished from the binder resin (E) by adsorbing to the surface of the pigment (A).

[0056] There are no particular restrictions on the dispersing resin (B), and known resins can be used. For example, urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyamino amidine salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinyl pyrrolidone; polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate ester-based, and the like can be mentioned.

[0057] (Dispersing resin (B1) having an acidic group) From the viewpoints of storage stability, developability, and suppression of foreign matters, the dispersing resin (B) preferably contains a dispersing resin (B1) having an acidic group.

[0058] Examples of the acidic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc. Among these, from the viewpoints of storage stability, developability, and suppression of foreign matters, a carboxyl group and a phosphoric acid group are preferable, and a carboxyl group is more preferable.

[0059] The acid value of the dispersion resin (B1) having an acidic group is preferably 30 to 250 mgKOH / g, more preferably 40 to 200 mgKOH / g, from the viewpoints of storage stability, developability, and suppression of foreign matters.

[0060] The dispersion resin (B1) having an acidic group can be used alone or in combination of two or more.

[0061] The content of the dispersion resin (B1) having an acidic group is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the pigment (A), from the viewpoints of storage stability, developability, and suppression of foreign matters.

[0062] The dispersion resin (B1) having an acidic group preferably contains either a dispersion resin (B1-1) having a carboxyl group-containing polyester moiety formed by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic dianhydrides and tricarboxylic anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer moiety formed by radical polymerization of a monomer, or a dispersion resin (B1-2) represented by the following general formula (5), and more preferably contains the dispersion resin (B1-1).

[0063] General formula (5) (HOOC-) m -R 2 -(-COO-[-R 4 -COO-] n -R 5 ) t (In the general formula (5), R 2 is a tetravalent tetracarboxylic acid compound residue, R 5 is a monoalcohol residue, R 4 is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t represents (4 - m).)

[0064] 〔Dispersion resin (B1-1)〕 The dispersion resin (B1-1) can be synthesized, for example, by the following method.

[0065] In the presence of a compound having two hydroxyl groups and one thiol group in the molecule (hereinafter also referred to as a thiol compound), a vinyl polymer having two hydroxyl groups at one end is synthesized by radical polymerization of a monomer having a polymerizable unsaturated group. Then, the hydroxyl group of the vinyl polymer is reacted with an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic dianhydrides and tricarboxylic anhydrides to obtain a dispersion resin (B1-1).

[0066] Further, a dispersion resin (B1-1) is obtained by radical polymerization of a monomer in the presence of a compound produced by reacting a hydroxyl group in a hydroxyl group-containing compound (excluding a vinyl polymer having hydroxyl groups at both ends) constituting the polyester moiety with an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic dianhydrides and tricarboxylic anhydrides.

[0067] Hereinafter, the polyester moiety having a carboxyl group will be described. The polyester moiety having a carboxyl group is obtained by the reaction of an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic dianhydrides and tricarboxylic anhydrides with a hydroxyl group in a hydroxyl group-containing compound.

[0068] The tetracarboxylic dianhydride is, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.Aliphatic tetracarboxylic dianhydrides such as 2-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol dianhydride trimellitate, propylene glycol dianhydride trimellitate, butylene glycol dianhydride trimellitate, 3,3’,4,4’-benzophenone tetracarboxylic dianhydride, 3,3’,4,4’-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3’,4,4’-biphenyl ether tetracarboxylic dianhydride, 3,3’,4,4’-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3’,4,4’-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4’-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4’-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4’-bis(3,4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3’,4,4’-perfluoroisopropylidene diphthalic dianhydride, 3,3’,4,4’-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4’-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4’-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride may be mentioned. Among these, aromatic tetracarboxylic dianhydrides are preferred from the viewpoint of adsorption to pigments..

[0069] The tetracarboxylic dianhydride is not limited to the compounds exemplified above, and any structure may be used as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Since the tetracarboxylic dianhydride forms a dispersion resin having two carboxyl groups per unit of the tetracarboxylic dianhydride by reaction with a hydroxyl group-containing compound, it is preferable as a component of the dispersion resin of the present invention from the viewpoint of pigment adsorptivity.

[0070] Examples of the tricarboxylic anhydride include aliphatic tricarboxylic anhydrides and aromatic tricarboxylic anhydrides.

[0071] Examples of the aliphatic tricarboxylic anhydride include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride, 1,3,4-cyclopentanetricarboxylic anhydride, and the like.

[0072] Examples of the aromatic tricarboxylic anhydride include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenyl ether tricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, or 3,4,4'-biphenylsulfonetricarboxylic anhydride, and the like. Among these, from the viewpoint of adsorptivity to pigments, it is an aromatic tricarboxylic anhydride.

[0073] The molar ratio of the acid anhydride group in one or more acid anhydrides selected from the above tetra-carboxylic dianhydride and tri-carboxylic anhydride to the hydroxyl group in the hydroxyl group-containing compound is preferably acid anhydride group / hydroxyl group = 0.5 to 1.5. When reacting at an appropriate ratio, it is easy to obtain a dispersion resin with good dispersibility.

[0074] The hydroxyl group-containing compound is preferably a polyol such as a diol having a plurality of hydroxyl groups among monools and polyols. The hydroxyl group in the polyol functions as a bonding starting point with the vinyl polymer portion. Examples of the polyol serving as a bonding starting point with the vinyl polymer portion include at least one hydroxyl group-containing compound selected from the group consisting of a compound having two hydroxyl groups and one thiol group in the molecule and a vinyl polymer having a hydroxyl group at one end. For example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol or 1-thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol, etc. can be mentioned.

[0075] From the viewpoint of the pattern shape, the following dispersion resin (B1-1-1) or dispersion resin (B1-1-2) is preferable as the dispersion resin (B1-1).

[0076] ≪Dispersion resin (B1-1-1)≫ The vinyl polymer portion of the dispersion resin (B1-1-1) is obtained by radical polymerization of (i) a monomer having at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group, (ii) a carboxyl group-containing monomer, and, if necessary, (iii) other monomers.

[0077] (i-1) [Hydroxyl group-containing monomer] Monomers having a hydroxyl group as a thermally crosslinkable group include (meth)acrylate monomers having a hydroxyl group, such as hydroxyalkyl (meth)acrylates like 2-hydroxyethyl (meth)acrylate, 2(or 3)-hydroxypropyl (meth)acrylate, 2(or 3or 4)-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates like ethyl-α-hydroxymethyl acrylate, or (meth)acrylamide monomers having a hydroxyl group, such as N-(hydroxyalkyl)(meth)acrylamides like N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, and N-(2-hydroxybutyl)(meth)acrylamide, or vinyl ether monomers having a hydroxyl group, such as hydroxyalkyl vinyl ethers like 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, and 2-(or 3-or 4-)hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as hydroxyalkyl allyl ethers like 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3-or 4-)hydroxybutyl allyl ether.

[0078] Also preferred are monomers obtained by adding an alkylene oxide and / or a lactone to the above-mentioned hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and a combination system of two or more of these. The bonding form when using two or more alkylene oxides in combination may be either random and / or block. Examples of the lactone to be added include δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these. It may also be one to which both an alkylene oxide and a lactone are added.

[0079] (i-2) [Oxetane group-containing monomer] Monomers having an oxetane group as a thermally crosslinkable group include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, [(meth)acryloyloxyalkyl]alkyloxetane, and the like. Among them, preferably, methyl (3-ethyloxetan-3-yl) methacrylate and the like can be mentioned. Examples of commercially available products include ETERNACOLL OXMA (methyl (3-ethyloxetan-3-yl) methacrylate) (manufactured by Ube Industries, Ltd.).

[0080] (i-3) [t-Butyl group-containing monomer] Monomers having a t-butyl group as a thermally crosslinkable functional group include, for example, t-butyl methacrylate, t-butyl acrylate, and the like.

[0081] (i-4) [Block isocyanate group-containing monomer] Monomers having a blocked isocyanate group as a thermally crosslinkable group include 2-(0-[1'-methylpropylideneamino]carboxamido)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and the like. Commercially available products include, for example, Karenz MOI-BM (2-(0-[1'-methylpropylideneamino]carboxamido)ethyl methacrylate) (manufactured by Showa Denko K.K.), Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko K.K.), and the like.

[0082] The content of the oxetane group-containing monomer, the t-butyl group-containing monomer, and the blocked isocyanate group-containing monomer is preferably 5 to 90% by mass, more preferably 20 to 60% by mass, based on the total monomers. If it is 5% by mass or more, a photosensitive composition excellent in resistance can be obtained due to the crosslinking effect. If it is 90% by mass or less, it is preferable because the stability of the composition is also good.

[0083] (ii) [Carboxyl group-containing monomer] Examples of the carboxyl group-containing monomer include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Among these, (meth)acrylic acid, which has good copolymerizability and is easily available, is preferable.

[0084] (iii) [Other monomers] For the vinyl polymer part of the dispersion resin (B1-1-1), other monomers other than the thermally crosslinkable group-containing monomer and the carboxyl group-containing monomer can be used. Examples of other monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate; Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, etc.; Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, etc.; Alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, etc.; N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, acryloylmorpholine, etc.; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, etc.; And nitriles such as (meth)acrylonitrile, etc. are included.

[0085] Also included are styrenes such as styrene, α-methylstyrene, etc., vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, etc., and fatty acid vinyls such as vinyl acetate, vinyl propionate, etc.

[0086] ≪Dispersion resin (B1-1-2)≫ The dispersion resin (B1-1-2) has a polymerizable unsaturated group in the vinyl polymer part.

[0087] The production method of the dispersed resin (B1-1-2) can be synthesized, for example, by reacting a compound having a (meth)acryloyl group, which is a polymerizable unsaturated group, and a functional group, with a polymer of a monomer containing a functional group-containing monomer that reacts with the functional group. For example, a reaction product of glycidyl methacrylate and a polymer having a hydroxyl group or a carboxyl group, a reaction product of methacryloyloxyethyl isocyanate and a polymer having a hydroxyl group or a carboxyl group, etc. can be mentioned. The polymer having a hydroxyl group or a carboxyl group can be obtained by subjecting a polymer having a glycidyl group to a ring-opening reaction with an acid anhydride compound, or by subjecting a polymer having an acid anhydride group to a ring-opening reaction. For example, the dispersed resin described in JP-A-2011-157416 can be mentioned.

[0088] [Dispersed resin (B1-2)] The dispersed resin (B1-2) is a dispersed resin represented by the following general formula (5), and specifically, it is the dispersed resin described in JP-A-2007-140487.

[0089] General formula (5) (HOOC - ) m -R 2 -(-COO - [-R 4 -COO - ] n -R 5 ) t (In the general formula (5), R 2 is a tetravalent tetracarboxylic acid compound residue, R 5 is a monoalcohol residue, R 4 is a lactone residue, m is 2 or 3, n is an integer from 1 to 50, and t represents (4 - m).)

[0090] [Dispersed resin (B2) having a basic group] From the viewpoint of storage stability, the photosensitive composition of the present invention preferably further contains a dispersed resin (B2) having a basic group.

[0091] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring.

[0092] The dispersion resin (B2) having a basic group preferably has at least one unit selected from the group represented by the following general formula (6), general formula (7), and general formula (8) as the basic group.

[0093] General formula (6)

Chemical formula

[0094] (In general formula (6), R 1 ~R 3 each independently represents a hydrogen atom or a linear or cyclic hydrocarbon group which may have a substituent, and two or more of R 1 ~R 3 may be bonded to each other to form a cyclic structure. R 4 represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y - represents a counter anion.)

[0095] General formula (7)

Chemical formula

[0096] (In general formula (7), R 5 , and R 6 each independently represents a hydrogen atom or a linear or cyclic hydrocarbon group which may have a substituent, and R 5 , and R 6 may be bonded to each other to form a cyclic structure. R 4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

[0097] General formula (8)

Chemical formula

[0098] (In general formula (8), R 7is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR 12 represents, and R 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R 8 , R 9 , R 10 , R 11 each independently represents a methyl group, an ethyl group, or a phenyl group. R 4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

[0099] R in the general formula (6) 1 ~R 3 are, for example, more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and particularly preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a benzyl group.

[0100] R in the general formula (7) 5 , R 6 are, for example, more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and particularly preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

[0101] In R of the general formula (8) 7 , the alkyl group having 1 to 18 carbon atoms includes, for example, linear, branched, and cyclic alkyl groups, and specifically includes a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group, and the like. The aryl group having 6 to 20 carbon atoms includes, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like. The aralkyl group having 7 to 12 carbon atoms includes, for example, a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms, and specifically includes a benzyl group, a phenethyl group, an α-methylbenzyl group, a 2-phenylpropan-2-yl group, and the like. The acyl group includes, for example, alkanoyl groups having 2 to 8 carbon atoms and aroyl groups, and specifically includes an acetyl group, a benzoyl group, etc. Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical are particularly preferable, a hydrogen atom and a methyl group are more preferable, and a methyl group is most preferable.

[0102] In General Formulas (6) to (8), the divalent linking group X is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R 13 -, -COO-R 14 -(wherein R 13 , and R 14 is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group), etc.), and preferably -COO-R 1 4 -. Further, in General Formula (6), the counter anion Y - is, for example, Cl - , Br - , I - , ClO 4 - , BF 4 - , CH 3 COO - , PF 6 - etc.

[0103] The quaternary ammonium base-containing monomer that is the precursor and partial structure of the general formula (6) is, for example, alkyl (meth)acrylate quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, (meth)acryloyloxymethylmorpholinoammonium chloride, etc.; alkyl (meth)acrylamide quaternary ammonium salts such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, (meth)acryloylaminoethyldimethylbenzylammonium chloride, etc.; dimethyldiallylammonium methyl sulfate, trimethylvinylphenylammonium chloride, etc.

[0104] The tertiary amine group-containing monomer that is the precursor and partial structure of the general formula (7) is, for example, (meth)acrylates having a tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate; (meth)acrylamides having a tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide, etc.

[0105] The monomer that is the precursor and partial structure of the general formula (8) is, for example, compounds represented by the following general formulas (8-1) to (8-11), etc.

[0106]

Chemical formula

[0107]

Chemical formula

[0108] In general formulas (8-1) to (8-11), R 4 represents hydrogen or a methyl group.

[0109] Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R 4 is a methyl group in general formula (8-1)), 1,2,2,6,6-pentamethylpiperidyl methacrylate (a compound in which R 4 is a methyl group in general formula (8-2)) are preferred, and particularly 1,2,2,6,6-pentamethylpiperidyl methacrylate is preferred.

[0110] The units represented by general formulas (6) to (8) may be contained alone or in combination of two or more, and may be contained in any of random copolymerization, block copolymerization or graft copolymerization modes, and it is more preferred to be contained in the form of a block copolymer.

[0111] The units represented by general formulas (6) to (8) are not particularly limited as long as they are structures obtained by copolymerizing copolymerizable monomers, and can be appropriately selected according to the application. Copolymerizable monomers are shown below.

[0112] For example, linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth), tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; Heterocyclic ring-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate; Aromatic ring-containing (meth)acrylates such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; (Poly)alkylene glycol monoalkyl ether (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octoxypolyethylene glycol - polypropylene glycol (meth)acrylate; Phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, parachlorophenylphenoxyethyl (meth)acrylate, parachlorophenylphenoxyethylene glycol (meth)acrylate, parachlorophenylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate and other (poly)alkylene glycol (meth)acrylates having an aromatic ring; 3-Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane and other (meth)acrylates having an alkyloxysilyl group; Trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate and other fluoroalkyl (meth)acrylates; (meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); (Meth)acrylamide, dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine and other N-substituted (meth)acrylamides; and nitriles such as (meth)acrylonitrile and the like. Also, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate and the like.

[0113] Furthermore, a carboxyl group-containing monomer can also be used in combination. Examples of the carboxyl group-containing monomer include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate.

[0114] Also, an amino group-containing monomer other than the units represented by general formulas (6) to (8) may be used in combination as long as the effects of the present invention are not impaired.

[0115] In addition, a resin in which a part of the basic group of the dispersion resin (B2) having a basic group is bonded to a compound represented by the following general formula (9) or (10) to form a salt can also be preferably used.

[0116] General formula (9)

Chemical formula

[0117] (In general formula (9), R 1 , and R 2 each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -O-R 4 , and R 4 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R 1 , and R 2 is a group containing a carbon atom.)

[0118] General formula (10)

Chem.

[0119] (In general formula (10), R 3 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -O-R 4 and R 4 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms.)

[0120] Examples of the compound represented by the general formula (9) include monobutyl phosphate, dibutyl phosphate, methyl phosphate, dibenzyl phosphate, diphenyl phosphate, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like.

[0121] Examples of the compound represented by the general formula (10) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethyl sulfate, monoethyl sulfate, mono-n-propyl sulfate, and the like. Hydrates such as p-toluenesulfonic acid monohydrate may also be used.

[0122] From the viewpoint of storage stability, the amine value of the dispersion resin (B2) having a basic group is preferably 20 to 250 mgKOH / g, more preferably 30 to 150 mgKOH / g.

[0123] The dispersion resin (B2) having a basic group can be used alone or in combination of two or more kinds.

[0124] From the viewpoint of storage stability, the content of the dispersion resin (B2) having a basic group is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the pigment (A).

[0125] From the viewpoints of storage stability and foreign matter suppression, the mass ratio of the dispersion resin (B1) having an acidic group to the dispersion resin (B2) having a basic group is preferably from 100:0 to 30:70, more preferably from 70:30 to 30:70.

[0126] From the viewpoints of storage stability and foreign matter suppression, the content of the dispersion resin (B) is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, based on 100 parts by mass of the pigment (A).

[0127] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0128] Examples of the polymerizable compound (C) include monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include vinyl groups of ethylenically unsaturated double bonds, (meth)allyl groups, (meth)acryloyl groups, and the like. The weight average molecular weight or formula weight of the polymerizable compound (C) is preferably less than 2,000.

[0129] The overlapping compound (C) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, urethane (meth)acrylate and other various acrylic acid esters and methacrylic acid esters, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

[0130] Commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330 manufactured by Nippon Kayaku Co., Ltd.; Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A manufactured by Toagosei Co., Ltd.; Biscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Industry Co., Ltd.; AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd.; NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd.; Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd.; EBECRYL 40, 130, 140, 145 manufactured by Daicel Ornex Co., Ltd.; OGSOL EA-0200, 0300 manufactured by Osaka Gas Chemical Co., Ltd., and the like.

[0131] The polymerizable compound (C) can be used alone or in combination of two or more.

[0132] The content of the polymerizable compound (C) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, in 100% by mass of the nonvolatile content of the photosensitive composition.

[0133] (Lactone-modified polymerizable compound) From the viewpoint of resistance, the photosensitive composition of the present invention preferably contains a lactone-modified polymerizable compound.

[0134] The lactone-modified polymerizable compound is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound is obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimetholmelamine, etc. with (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound is preferably a compound represented by the following general formula (11).

[0135] General formula (11)

Chemical formula

[0136] In general formula (11), all six Rs are groups represented by the following general formula (12), or 1 to 5 of the six Rs are groups represented by the following general formula (12), and the rest are groups represented by the following general formula (13).

[0137] General formula (12)

Chemical formula

[0138] In general formula (12), R 1 represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond that binds to the oxygen atom of general formula (11).

[0139] General formula (13)

Chemical formula

[0140] In general formula (13), R 1 represents a hydrogen atom or a methyl group, and * is a bond that binds to the oxygen atom of general formula (11).

[0141] The lactone-modified polymerizable compound is commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. DPCA-20 (in the above general formulas (11) to (13), m = 1, the number of groups represented by the general formula (12) = 2, R 1 is a compound in which all are hydrogen atoms), DPCA-30 (in the above general formulas (11) to (13), m = 1, the number of groups represented by the general formula (12) = 3, R 1 is a compound in which all are hydrogen atoms), DPCA-60 (in the above general formulas (11) to (13), m = 1, the number of groups represented by the general formula (12) = 6, R 1 is a compound in which all are hydrogen atoms), DPCA-120 (in the above general formulas (11) to (13), m = 2, the number of groups represented by the general formula (12) = 6, R 1 is a compound in which all are hydrogen atoms), and the like can be mentioned.

[0142] From the viewpoint of resistance, the lactone-modified polymerizable compound is preferably a compound in which, in the above general formulas (11) to (13), m = 1, the number of groups represented by the general formula (12) = 2 to 6, and R 1 are all hydrogen atoms. More preferably, in the above general formulas (11) to (13), m = 1, the number of groups represented by the general formula (12) = 2 or 3, and R 1 are all hydrogen atoms.

[0143] From the viewpoint of resistance, the content of the lactone-modified polymerizable compound is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass in 100% by mass of the polymerizable compound (C).

[0144] (Polymerizable compound having an acidic group) From the viewpoints of development residue and pattern shape, the photosensitive composition of the present invention preferably contains a polymerizable compound having an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. Among these, a carboxyl group is preferable.

[0145] Polymerizable compounds having an acidic group include, for example, esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates with (meth)acrylic acid, and esterified products of dicarboxylic acids; esterified products of polycarboxylic acids and monohydroxyalkyl (meth)acrylates, etc. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, etc. Examples of polycarboxylic acids include trimellitic acid, pyromellitic acid, etc. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, etc.

[0146] Commercially available products of polymerizable compounds having an acidic group include Biscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521, etc. manufactured by Toagosei Co., Ltd.

[0147] From the viewpoints of development residue and pattern shape, the content of the polymerizable compound having an acidic group is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass in 100% by mass of the polymerizable compound (C).

[0148] (Polymerizable compound having a urethane bond) From the viewpoint of pattern shape, the photosensitive composition of the present invention preferably contains a polymerizable compound having a urethane bond.

[0149] Polymerizable compounds having a urethane bond include, for example, urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting with a (meth)acrylate having a hydroxyl group.

[0150] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy (meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0151] Examples of the polyfunctional isocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate, which are aromatic diisocyanates; trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, which are aliphatic diisocyanates; isophorone diisocyanate, which is an alicyclic diisocyanate; and burette bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies, and the like thereof.

[0152] From the viewpoint of developability, the polymerizable compound having a urethane bond can further have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and the like. Among them, a carboxyl group is preferable.

[0153] A method for introducing an acidic group into a polymerizable compound having a urethane bond is, for example, first reacting the (meth)acrylate having the above hydroxyl group with the above polyfunctional isocyanate. Next, it can be synthesized by a method of adding a mercapto compound having a carboxyl group to the product.

[0154] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

[0155] From the viewpoint of the pattern shape, the number of polymerizable unsaturated groups of the polymerizable compound having a urethane bond is preferably 3 to 15, more preferably 5 to 12.

[0156] From the viewpoint of the pattern shape, the content of the polymerizable compound having a urethane bond is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass in 100% by mass of the polymerizable compound (C).

[0157] From the viewpoints of development residue, pattern shape, and resistance, the photosensitive composition of the present invention preferably contains, as the polymerizable compound (C), a polymerizable compound having an acidic group and a lactone-modified polymerizable compound or / and a polymerizable compound having a urethane bond.

[0158] [Binder resin (E)] The photosensitive composition of the present invention contains a binder resin (E). Thereby, the resistance such as heat resistance and chemical resistance of the cured film is improved.

[0159] The binder resin (E) is not particularly limited, and known resins can be used.

[0160] Binder resin (E) can be classified into a non-photosensitive binder resin and a photosensitive binder resin, and from the viewpoint of developability, it preferably has an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a phenolic hydroxyl group, etc. Among these, a carboxyl group is preferred. Also, the binder resin (E) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

[0161] (Non-photosensitive binder resin) Examples of the non-photosensitive binder resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / (anhydrous) maleic acid copolymer, etc. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferred.

[0162] (Photosensitive binder resin) The photosensitive binder resin is a binder resin having a polymerizable unsaturated group. The photosensitive binder resin is preferably a resin synthesized by the method of (i) or (ii) shown below. By curing with active energy rays, the resin undergoes three-dimensional crosslinking to improve the crosslinking density and chemical resistance.

[0163] [Method (i)] Method (i) is, for example, first, a polymer of an epoxy group-containing monomer and other monomers is synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the generated hydroxyl group to obtain a photosensitive binder resin.

[0164] Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0165] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO) modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO modified (meth)acrylate of phenol, EO or propylene oxide (PO) modified (meth)acrylate of p-cumylphenol, EO modified (meth)acrylate of nonylphenol, PO modified (meth)acrylate of nonylphenol, etc. (meth)acrylates; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine; Styrenes such as styrene or α-methylstyrene; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Vinyl fatty acids such as vinyl acetate or vinyl propionate; N-substituted maleimides such as cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine; Phosphate ester group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl groups of the hydroxyl group-containing monomers described below.

[0166] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted products of (meth)acrylic acid.

[0167] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. Further, if necessary, tricarboxylic acid anhydrides such as trimellitic anhydride and tetracarboxylic dianhydrides such as pyromellitic anhydride can be used to hydrolyze the remaining anhydride groups.

[0168] Also, as a method similar to method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized. Next, an epoxy group-containing monomer is added to a part of the carboxyl groups of the polymer to obtain a photosensitive binder resin.

[0169] [Method (ii)] Method (ii) is, for example, a method of synthesizing a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers. Next, an isocyanate group of an isocyanate group-containing monomer is reacted with the hydroxyl groups of the polymer.

[0170] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Further, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylate obtained by addition of polyγ-butyrolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc. are also included. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferable in terms of being less likely to generate foreign substances in the film. Also, glycerol mono(meth)acrylate is preferable in terms of photosensitivity.

[0171] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

[0172] As the monocarboxyl group-containing monomer and other monomers, those described above can be used.

[0173] The raw materials used for the synthesis of the photosensitive binder resin can be used alone or in combination of two or more.

[0174] The binder resin (E) can be used alone or in combination of two or more.

[0175] The weight average molecular weight (Mw) of the binder resin (E) is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and particularly preferably from 4,000 to 20,000. Further, the value of Mw / Mn is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves the adhesion to the substrate and the developability.

[0176] The acid value of the binder resin (E) is preferably from 50 to 200 mgKOH / g, more preferably from 70 to 180 mgKOH / g, and even more preferably from 90 to 170 mgKOH / g. An appropriate acid value improves the adhesion to the substrate and the developability.

[0177] The content of the binder resin (E) is preferably from 20 to 400 parts by mass, more preferably from 50 to 250 parts by mass, based on 100 parts by mass of the pigment (A).

[0178] [Sensitizer (F)] From the viewpoint of the pattern shape, the photosensitive composition of the present invention preferably contains a sensitizer (F).

[0179] The sensitizer (F) includes, for example, chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, polymethine dyes such as cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyllin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, or benzophenone compounds, etc. Among these, from the viewpoint of the pattern shape, thioxanthone compounds (F1) or benzophenone compounds (F2) are preferable.

[0180] (Thioxanthone compounds (F1)) Examples of the thioxanthone compounds (F1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferable.

[0181] (Benzophenone compounds (F2)) Benzophenone compounds (F2) include, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, and the like. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0182] The sensitizer (F) can be used alone or in combination of two or more.

[0183] From the viewpoint of the pattern shape, the content of the sensitizer (F) is preferably 10 to 300 parts by mass, more preferably 20 to 250 parts by mass, and particularly preferably 30 to 200 parts by mass with respect to 100 parts by mass of the photoinitiator (D).

[0184] [Dye derivative (G)] The photosensitive composition of the present invention can contain a dye derivative (G).

[0185] The dye derivative (G) is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. The dye derivative (G) includes, for example, compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group and a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group and a phthalimidalkyl group. Organic dyes include, for example, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, and polyazo.

[0186] Specifically, as diketopyrrolopyrrole-based pigment derivatives, there are JP-A No. 2001-220520, WO 2009 / 081930, WO 2011 / 052617, WO 2012 / 102399, JP-A No. 2017-156397; as phthalocyanine-based pigment derivatives, there are JP-A No. 2007-226161, WO 2016 / 163351, JP-A No. 2017-165820, Patent No. 5753266; as anthraquinone-based pigment derivatives, there are JP-A No. 63-264674, JP-A No. 09-272812, JP-A No. 10-245501, JP-A No. 10-265697, JP-A No. 2007-079094, WO 2009 / 025325; as quinacridone-based pigment derivatives, there are JP-A No. 48-54128, JP-A No. 03-9961, JP-A No. 2000-273383; as dioxazine-based pigment derivatives, there is JP-A No. 2011-162662; as thiazine indigo-based pigment derivatives, there is JP-A No. 2007-314785; as triazine-based pigment derivatives, there are JP-A No. 61-246261, JP-A No. 11-199796, JP-A No. 2003-165922, JP-A No. 2003-168208, JP-A No. 2004-217842, JP-A No. 2007-314681; as benzoisoindole-based pigment derivatives, there is JP-A No. 2009-57478; as quinophthalone-based pigment derivatives, there are JP-A No. 2003-167112, JP-A No. 2006-291194, JP-A No. 2008-31281, JP-A No. 2012-226110; as naphthol-based pigment derivatives, there are JP-A No. 2012-208329, JP-A No. 2014-5439; as azo-based pigment derivatives, there are JP-A No. 2001-172520, JP-A No. 2012-172092; as acidic substituents, there is JP-A No. 2004-307854; as basic substituents, there are JP-A No. 2002-201377, JP-A No. 2003-171594, JP-A No. 2005-181383, JP-A No. 2005-213404, etc. Known pigment derivatives described therein can be mentioned.In these documents, the dye derivatives may be described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds. However, a compound having a substituent such as an acidic group, a basic group, or a neutral group in the above-described organic dye residue is synonymous with a dye derivative.

[0187] The dye derivative (G) can be used alone or in combination of two or more.

[0188] The content of the dye derivative (G) is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, with respect to 100 parts by mass of the pigment (A).

[0189] [Dye (H)] The photosensitive composition of the present invention can contain a dye (H).

[0190] The dye (H) is not particularly limited, and known dyes can be used. For example, acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. can be mentioned. In addition, derivatives thereof and lake pigments obtained by lake-forming dyes are also mentioned.

[0191] The acidic dye preferably has an acidic group such as a sulfonic acid or a carboxylic acid. Further, a salt-forming compound which is a salt of an acidic dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. Further, a salt-forming compound which is a salt of a resin component having these functional groups and an acidic dye is also preferable. Further, the salt-forming compound is likely to obtain a photosensitive composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification into a sulfonic acid amide compound. In addition, a salt-forming compound of an acidic dye and a compound having an onium base is also preferable because of its excellent resistance (light resistance, solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

[0192] Basic dyes can be used as they are, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. The salt-forming compounds of basic dyes are preferred because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, among the salt-forming compounds of basic dyes, the anionic components that act as counterions are organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, anion compounds having a conjugated base of an organic acid having a halogenated hydrocarbon group, and salt-forming compounds formed by salting with acid dyes. Note that the salt-forming compound has better resistance when it contains a polymerizable unsaturated group in the molecule.

[0193] The chemical structure of the dye can be, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (such as oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and pigment structures derived from dyes selected from metal complex dyes thereof, etc., but are not particularly limited thereto.

[0194] Among these dye structures, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferable.

[0195] [Thermosetting compound (I)] The photosensitive composition of the present invention can contain a thermosetting compound (I). Thereby, the thermosetting compound (I) reacts in the heating step, and the crosslinking density increases, so the heat resistance is improved.

[0196] The thermosetting compound (I) may be a low-molecular compound or a high-molecular compound such as a resin. Examples of the thermosetting compound (I) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferable.

[0197] [Epoxy compound (I1)] The epoxy compound (I1) includes, for example, polycondensates of bisphenols (such as bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (such as phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (such as formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthalaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polymers of phenols and various diene compounds (such as dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α’,α’-benzenedimethanol, biphenyldimethanol, α,α,α’,α’-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as α,α’-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

[0198] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, Inc., EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020 manufactured by Japan Epoxy Resins Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154, Celloxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S, etc. manufactured by Nissan Chemical Industries, Ltd.

[0199] The content of the epoxy compound (I1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile components of the photosensitive composition.

[0200] (Oxetane compound (I2)) The oxetane compound (I2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0201] Examples of the monofunctional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, and the like.

[0202] Commercially available products include, for example, OXE-10, 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 212 manufactured by Toagosei Co., Ltd., and the like.

[0203] The bifunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl)ether, and the like.

[0204] Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0205] Oxetane compounds having three or more functional groups include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, oxetane-modified phenol novolak resins described in Japanese Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0206] The content of the oxetane compound (I2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0207] Melamine compounds are compounds having a melamine ring structure. Melamine compounds are preferably methylol-type or ether-type compounds, and more preferably melamine compounds having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Appropriate numbers of methylol groups and ether groups make it easy to obtain heat resistance without excess or deficiency.

[0208] Commercially available products include, for example, Nikkalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 manufactured by Sanwa Chemical Co., Ltd., Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Sytrex Industries Co., Ltd., and the like.

[0209] Among these, Nikkalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 manufactured by Nippon Sytrex Industries Co., Ltd., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferable in terms of increasing the crosslink density.

[0210] The thermosetting compound (I) can be used alone or in combination of two or more.

[0211] [Hardener (curing accelerator)] In order to assist the curing of the thermosetting compound (I), a curing agent (curing accelerator) can be used in combination with the photosensitive composition of the present invention. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0212] The curing agent can be used alone or in combination of two or more.

[0213] The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (I).

[0214] [Thiol-based chain transfer agent (J)] The photosensitive composition of the present invention can contain a thiol-based chain transfer agent (J). When the thiol-based chain transfer agent (J) is used in combination with the photopolymerization initiator (D), thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the photosensitivity of the photosensitive composition is improved.

[0215] The thiol-based chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), and more preferably a polyfunctional thiol having four or more thiol groups. As the number of functional groups increases, it becomes easier to photocure from the surface to the deepest part of the film.

[0216] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc. are mentioned.

[0217] The thiol-based chain transfer agent (J) can be used alone or in combination of two or more.

[0218] The content of the thiol-based chain transfer agent (J) is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0219] [Polymerization inhibitor (K)] The photosensitive composition of the present invention can contain a polymerization inhibitor (K).

[0220] The polymerization inhibitor (K) is, for example, an alkylcatechol compound such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol, etc.; an alkylresorcinol compound such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, etc.; an alkylhydroquinone compound such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, etc.; a phosphine compound such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc.; a phosphine oxide compound such as trioctylphosphine oxide, triphenylphosphine oxide, etc.; a phosphite compound such as triphenylphosphite, trisnonylphenylphosphite, etc.; pyrogallol, phloroglucin, etc.

[0221] The content of the polymerization inhibitor (K) is preferably 0.01 to 0.4% by mass in 100% by mass of the non-volatile components of the photosensitive composition.

[0222] [Ultraviolet absorber (L)] The photosensitive composition of the present invention can contain an ultraviolet absorber (L).

[0223] The ultraviolet absorber (L) is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0224] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0225] Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, Ltd., Adeka Stab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA Corporation, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

[0226] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and the like.

[0227] Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, Ltd., Adeka Stab LA-46, LA-F70 manufactured by ADEKA Corporation, CYASORB UV-1164 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0228] Benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0229] Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cypro Kasei Co., Ltd., Adeka Stab 1413 manufactured by ADEKA Corporation, UV-12 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0230] Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0231] The content of the ultraviolet absorber (L) is preferably 5 to 70% by mass in the total of 100% by mass of the photopolymerization initiator (D) and the ultraviolet absorber (L).

[0232] [Antioxidant (M)] The photosensitive composition of the present invention can contain an antioxidant (M).

[0233] The antioxidant (M) prevents yellowing caused by oxidation of the photoinitiator (D) and the thermosetting compound (I) in the photosensitive composition during heat curing or the heat treatment during ITO annealing. In particular, when the pigment (A) concentration of the photosensitive composition is high, the content of the polymerizable compound (C) relatively decreases. Therefore, if the amount of the photoinitiator (D) is increased or a thermosetting compound is blended to cope with this, the cured film is likely to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented. The antioxidant (M) is preferably a compound that does not contain a halogen atom.

[0234] Examples of the antioxidant (M) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0235] Hindered phenolic antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and the like can be mentioned.

[0236] Commercially available products include, for example, Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, KEMINOX 101, 179, 76, 9425 manufactured by Chemipro, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, and Cyanox CY-1790, CY-2777 manufactured by Sankyo Chemical, etc.

[0237] Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, the polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], the ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis〔4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl〕-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyrperidyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyrperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0238] Commercially available products include, for example, AdekaStab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd.; Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Ltd.; and Cyasorb-UV-3346, UV-3529, UV-3853 manufactured by Sankyo Chemical Co., Ltd., etc.

[0239] Phosphorus-based antioxidants include, for example, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyldiphosphonite, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisononylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylenebis(4,6-di-t-butylphenyl) phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc.

[0240] Commercially available products include, for example, Adeka Stub PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation; IRGAFOS 168 manufactured by BASF Japan Ltd.; Hostanox P-EPQ manufactured by Clariant Chemicals, etc.

[0241] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diyl bis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc.

[0242] Commercially available products include, for example, Adeka Stub AO-412S, AO-503 manufactured by ADEKA Corporation; Keminox PLS manufactured by Chemipro Kasei Co., Ltd., etc.

[0243] The antioxidant (M) can be used alone or in combination of two or more.

[0244] The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile components of the photosensitive composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are improved.

[0245] [Leveling agent (N)] The photosensitive composition of the present invention can contain a leveling agent (N). Thereby, the wettability and drying property with respect to the substrate during coating are further improved.

[0246] Examples of the leveling agent (N) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc.

[0247] Silicone surfactants include, for example, linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or terminals.

[0248] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK Chemie; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning; X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0249] Fluorine-based surfactants include, for example, surfactants or leveling agents having a fluorocarbon chain.

[0250] Commercially available products include, for example, Surfron S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation; FC-4430, 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; 602A of Phthalgent manufactured by Neos Corporation.

[0251] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrylated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, and the like.

[0252] Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amite 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical's (meth)acrylic acid-based (co)polymers Polyflow - No. 75, No. 90, No. 95, etc.

[0253] Examples of cationic surfactants include alkylamine salts and alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, and ethylene oxide adducts thereof.

[0254] Commercially available products include, for example, Kao's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0255] Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphoric acid esters, and the like.

[0256] Commercially available products include, for example, Furgent 100 and 150 manufactured by Neos Co., Ltd., Adeka Hope YES-25 manufactured by ADEKA Corporation, Adeka Cole TS-230E, PS-440E, EC-8600, etc.

[0257] Amphoteric surfactants include, for example, alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocoamidopropyl betaine, stearyl betaine, alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

[0258] Commercially available products include, for example, Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.

[0259] The leveling agent (N) can be used alone or in combination of two or more.

[0260] The content of the leveling agent (N) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the balance between the coatability and the adhesiveness of the photosensitive composition is further improved.

[0261] [Storage stabilizer (O)] The photosensitive composition of the present invention can contain a storage stabilizer (O). Thereby, the viscosity of the photosensitive composition over time is stabilized.

[0262] The storage stabilizer (O) includes, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphites.

[0263] The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the pigment (A).

[0264] [Adhesion improver (P)] The photosensitive composition of the present invention can contain an adhesion improver (P). Thereby, the adhesion between the cured film and the substrate is improved. Also, it becomes easier to form a pattern with a narrow width by the photolithography method.

[0265] The adhesion promoter (P) includes, for example, silane coupling agents. Silane coupling agents include, for example, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; aminosilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and the hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptans such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatopropyltriethoxysilane, etc.

[0266] The adhesion promoter (P) can be used alone or in combination of two or more.

[0267] The content of the adhesion promoter (P) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the pigment (A).

[0268] [Organic solvent (Q)] The photosensitive composition of the present invention can contain an organic solvent (Q).

[0269] The organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters and the like. Among these, from the viewpoints of the dispersibility of the pigment and the solubility of the alkali-soluble resin, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0270] The organic solvent (Q) can be used alone or in combination of two or more.

[0271] [Content of specific metal element] In the photosensitive composition of the present invention, the total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive composition is preferably 500 mass ppm or less.

[0272] When the total amount of the specific metal element is within the above range in the photosensitive composition, it is excellent in dispersion stability and sensitivity even after storage over time. In addition, a color filter made using a photosensitive composition with the total amount of the specific metal element within the above range has excellent heat resistance and generates few foreign substances even when heated.

[0273] The total amount of the specific metal element contained in the photosensitive composition is more preferably 300 mass ppm or less, and particularly preferably 200 mass ppm or less. The lower limit of the total amount of the specific metal element is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 5 mass ppm or more. Within the above range, a photosensitive composition can be obtained that can suppress costs, has excellent storage stability, and can form a color filter with few foreign substances generated.

[0274] The method for reducing the specific metal element contained in the photosensitive composition is not particularly limited, but since the specific metal element is contained in a large amount in the pigment (A), it is preferable to remove the specific metal element from the pigment (A). In addition, since it is also mixed in from the apparatus for manufacturing the photosensitive composition, it is also preferable to suppress the mixing in from the apparatus.

[0275] The method for reducing and removing the specific metal element contained in the pigment (A) is not particularly limited, and known methods can be used. For example, as a method for avoiding mixing in from the apparatus during the manufacturing process, the methods described in JP-A-2010-83997, JP-A-2018-36521, etc. can be mentioned. Also, for example, as a method for removing from the pigment (A), the methods described in JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, JP-A-2010-83997, etc. can be mentioned. Among these, a method of washing the pigment (A) with water having a low content of the specific metal element, for example, ion-exchanged water, etc., is preferable.

[0276] The method for washing the pigment (A) is not particularly limited, and known methods can be used. For example, after synthesis, the pigment (A) is put into a container filled with ion-exchanged water and stirred. After stirring for a certain period of time, it is filtered with a filter press to separate the pigment (A) from the ion-exchanged water. This operation is repeated until the content of the specific metal element reaches the desired value. The washing is preferably carried out while heating. Thereafter, the pigment (A) is dried with hot air and pulverized.

[0277] The content of the specific metal element can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0278] From the viewpoints of storage stability and suppression of foreign matter generation, the photosensitive composition of the present invention preferably also reduces the content of metal elements other than the specific metal element. Examples of metals other than the specific metal element include Mn, Cs, Ti, Co, Ni, Si, Pd, etc.

[0279] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less contained in the photosensitive composition.

[0280] When the photosensitive composition has a water content within the above range, it has excellent dispersion stability and sensitivity even after storage over time.

[0281] The water content contained in the photosensitive composition is more preferably 1.8% by mass or less, and particularly preferably 1.6% by mass or less. Also, the lower limit of the water content is preferably as low as possible, and there is no particular limitation. Within the above range, it has excellent dispersion stability and sensitivity even after storage over time.

[0282] The method for controlling the water content is not particularly limited, and known methods can be used. For example, a method of producing a photosensitive composition while blowing dry air, an inert gas, or a mixed gas thereof, a method of producing in a sealed container replaced with a dry inert gas, or a method of adding a molecular sieve for dehydration after production can be mentioned. Further, using sufficiently dried raw materials can also be mentioned. Among them, a method of producing while blowing dry air or an inert gas, and a method of producing in a sealed container replaced with a dry inert gas are preferable.

[0283] The water content can be measured by a known method such as the Karl Fischer method.

[0284] Although the mechanism by which the photosensitive composition having the above configuration can solve the problems of the present invention is not clear, it is presumed as follows.

[0285] It is presumed that by reducing the amount of the specific metal element and the amount of water, the ionization of the specific metal element is suppressed, and the reaction during storage over time with the photoinitiator is suppressed. Further, it is presumed that the dispersion resin (B1) having an acidic group forms a salt with the ionized specific metal element, thereby suppressing the reaction during storage over time with the photoinitiator.

[0286] [Method for producing a photosensitive composition] The photosensitive composition of the present invention can be produced, for example, by adding a pigment (A), a dispersion resin (B), a dye derivative (G), an organic solvent (Q), etc., and performing a dispersion treatment to produce a dispersion. Then, a polymerizable compound (C), a photoinitiator (D), a binder resin (E), etc. are blended and mixed with the dispersion. The timing of blending each material is arbitrary. Further, the dispersion step can be performed multiple times.

[0287] Examples of the disperser for performing the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

[0288] The average dispersed particle diameter (secondary particle diameter) of the pigment in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. When the particle diameter is appropriate, a photosensitive composition with high dispersion stability can be easily obtained.

[0289] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using the Microtrac UPA-EX150 of Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power spectrum method), the particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set as the average diameter. As the dilution solvent for measurement, the organic solvents used for dispersion are each used, and it is preferable to measure the sample immediately after sample preparation for the sample treated with ultrasonic waves because less variation in results is likely to be obtained.

[0290] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust by means such as centrifugation, filtration through a sintered filter or a membrane filter. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0291] <Optical filter> The optical filter of the present invention includes a substrate and filter segments formed from the photosensitive composition of the present invention. The optical filter can be used for various applications. In this specification, the optical filter is preferably a color filter. In the case of a color filter, the filter segments have a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of the pigment (A) to be used. Instead of or in addition to the above filter segments, it can also have a magenta color filter segment, a cyan color filter segment, a yellow color filter segment, a white filter segment, and a black filter segment. It can also have a clear filter using extender pigments such as titanium oxide and silica. The substrate includes a transparent substrate and a reflective substrate. The transparent substrate includes, for example, a glass substrate. The reflective substrate includes, for example, a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0292] [Method for manufacturing an optical filter] The method for manufacturing an optical filter can be manufactured, for example, by performing the following steps: (1) applying a photosensitive composition on a substrate to form a layer (film) of the composition; (2) exposing the layer in a pattern through a mask; (3) alkali-developing the unexposed portion to form a patterned cured film; and (4) heat-treating (post-baking) the pattern.

[0293] Hereinafter, the method for manufacturing an optical filter will be described in detail. (Step (1)) In step (1) of forming a layer of the composition, the photosensitive composition is applied on the substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and dried (pre-baked) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, hot plate, etc., as necessary. The substrate includes, for example, a glass substrate, a silicon substrate, etc. The silicon substrate may have, for example, an imaging element such as a CCD or a CMOS formed on its surface. Further, a undercoat layer may be provided on the substrate as necessary to improve adhesion with an upper layer, prevent diffusion of substances, and planarize the substrate surface. The film thickness of the layer is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm.

[0294] (Step (2)) In the exposure step, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper, etc. Thereby, a cured film is obtained. The radiation used for exposure includes, for example, ultraviolet rays such as g-line, h-line, i-line, etc.

[0295] (Step (3)) The cured film obtained in step (2) can be developed with an alkali to elute the composition layer in the unexposed portion into an aqueous alkali solution, leaving only the cured portion to obtain a patterned cured film. Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed, and the residual film rate after development is improved.

[0296] Examples of the development method include dip method, spray method, paddle method, etc. The development temperature is preferably 15 to 40°C. After alkali development, it is preferably washed with pure water.

[0297] (Step (4)) The heat treatment (post-bake) sufficiently cures the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 100 to 300°C, more preferably 150 to 250°C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

[0298] <Image display device> The image display device of the present invention includes the optical filter of the present invention. Examples of the image display device include a liquid crystal display, an organic EL display, etc. The form used in the image display device only needs to function as an image display device and is not particularly limited. For example, the configurations described in "Next-generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Kogyo Chosa Kai, Inc., in 1994) can be mentioned. For the definition of the image display device and the details of each image display device, refer to, for example, "Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosa Kai, Ltd. in 1990)", "Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)", etc.

[0299] <Solid-state imaging device> The solid-state imaging device of the present invention includes the optical filter of the present invention. The form used for the solid-state imaging device is not particularly limited. For example, on a substrate, it has a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc., and has a light-shielding film with only the light-receiving part of the photodiode opened on the photodiodes and the transfer electrodes, and has a device protection film made of silicon nitride, etc., formed so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film, and has a configuration with a filter on the device protection film. Further, a configuration having condensing means (for example, a microlens, etc. The same applies hereinafter) on the device protection film and under the filter (on the side close to the substrate), or a configuration having condensing means on the filter may be used. Also, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state imaging device of the present invention can be used for various applications such as, for example, a digital camera, an electronic device having an imaging function (such as a mobile phone, a smartphone, etc.), an in-vehicle camera, a surveillance camera, a biometric authentication sensor, etc.

Example

[0300] Hereinafter, the present invention will be described more specifically with examples. However, the present invention is not limited thereto. Note that "parts" means "parts by mass" and "%" means "% by mass". Also, in the present invention, the non-volatile content or the non-volatile content concentration refers to the mass residue after standing in an oven at 230 °C for 30 minutes.

[0301] Prior to the examples, each measurement method will be described.

[0302] (Number-average molecular weight of the resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as the apparatus, two separation columns were connected in series, and for both packing materials, two "TSK-GEL SUPER HZM-N" were connected in series and used. The oven temperature was 40 °C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent and 20 microliters were injected. The average molecular weight is a polystyrene conversion value.

[0303] (Acid value of the resin) To 0.5 - 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to dissolve uniformly. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was performed using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, from the acid value of the resin solution and the non-volatile content concentration of the resin solution, the acid value per non-volatile content of the resin was calculated.

[0304] (Amine value of the resin) The amine value of the resin is the value obtained by converting the total measured amine value (mgKOH / g) to non-volatile content basis in accordance with the method of ASTM D 2074.

[0305] (Measurement of the content of specific metal elements) Using an ICP emission spectroscopic analyzer (ICPE-9800 manufactured by Shimadzu Corporation), the contents of Li, Na, K, Mg, Ca, Fe, and Cr contained in the photosensitive composition were measured.

[0306] (Measurement of the water content) Using a Karl Fischer titrator (KF-06 type, a volumetric titration type water content measuring device manufactured by Mitsubishi Chemical Corporation), the water content contained in the photosensitive composition was measured.

[0307] (Manufacture of pigment (A)) (Micronized Pigment (A-1)) 100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60°C for 6 hours. Next, this kneaded product was poured into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70°C, and then filtered (washing step). The washing step was repeated to remove sodium chloride and diethylene glycol. Thereafter, it was dried at 80°C for one day and night to obtain the micronized pigment (A-1).

[0308] (Micronized Pigment (A-2)) 100 parts of C.I. Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60°C for 6 hours. Next, this kneaded product was poured into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70°C, and then filtered (washing step). The washing step was repeated to remove sodium chloride and diethylene glycol. Thereafter, it was dried at 80°C for one day and night to obtain the micronized pigment (A-2).

[0309] (Micronized Pigment (A-3)) 100 parts of C.I. Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours. Next, this kneaded product was poured into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70°C, and then filtered (washing step). The washing step was repeated to remove sodium chloride and diethylene glycol. Thereafter, it was dried at 80°C for one day and night to obtain the micronized pigment (A-3).

[0310] (Micronized Pigment (A-4)) According to the examples of Japanese Patent Application Laid-Open No. 2012-226110, the pigment (A-4) of the following chemical formula (14) was obtained. 100 parts of the pigment (A-4), 700 parts of ground sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70°C, and then filtered (washing step). The washing step was repeated to remove sodium chloride and diethylene glycol. Thereafter, it was dried at 80°C for a whole day and night to obtain the micronized pigment (A-4).

[0311] Chemical formula (14) [Chemical formula]

[0312] (Micronized pigment (A-5)) 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine were charged into a 300 mL flask. The temperature was raised to 130°C over 40 hours, taken out in water, and then filtered to obtain a zinc phthalocyanine halide compound having an average of 12.71 halogen atoms per molecule, of which the average number of bromine atoms was 10.22 and the average number of chlorine atoms was 2.49. 100 parts of the zinc phthalocyanine halide compound, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70°C for 6 hours. Next, this kneaded product was put into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70°C, and then filtered (washing step). The washing step was repeated to remove sodium chloride and diethylene glycol. Thereafter, it was dried at 80°C for a whole day and night to obtain the micronized pigment (A-5).

[0313] (Micronized pigment (A-6)) According to the examples of JP-A-2017-111398, the pigment (A-6) of the following chemical formula (15) was obtained. 100 parts of the pigment (A-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70°C for 6 hours. This kneaded product was poured into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70°C, and then filtered (washing step). The washing step was repeated to remove sodium chloride and diethylene glycol. Thereafter, it was dried at 80°C for one day and night and pulverized to obtain a refined pigment (A-6).

[0314] Chemical formula (15) [Chemical formula]

[0315] <Production of dispersion resin (B)> (Solution of dispersion resin (B1-1) having an acidic group) Into a reaction vessel equipped with a gas introduction tube, a temperature controller, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred to 50°C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was added while reacting for 7 hours. It was confirmed by non-volatile content measurement that 95% of the reaction had occurred. 19 parts of pyromellitic dianhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. PGMAc was added for dilution so that the non-volatile content became 30% by non-volatile content measurement, and a solution of dispersion resin (B1-1) having an acidic group with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500 was obtained.

[0316] (Dispersion resin (B1-1-2) solution having an acidic group) Into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were charged. After replacing with nitrogen gas, the mixture was reacted at 120 °C for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged. The inside of the reaction vessel was heated to 80 °C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours (second step). It was confirmed by non-volatile content measurement that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm-1 based on the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a dispersion resin (B1-1-2) solution having an acidic group with a non-volatile content of 30%. The acid value of the obtained dispersion resin (B1-1-2) having an acidic group was 68 mgKOH / g, the unsaturated double bond equivalent was 1,593, and the weight average molecular weight was 13,000.

[0317] (Dispersion resin (B2-1) solution having a basicity) Into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged. While flowing nitrogen, the mixture was stirred at 50 °C for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FUNCRYL FA-711MM) as the second block (A block) monomer were added to this reactor, and the mixture was stirred while maintaining the temperature at 110 °C in a nitrogen atmosphere to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content. The reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added for dilution so that the non-volatile content became 30% in the non-volatile content measurement, and a basic dispersion resin (B2-1) solution with an amine value of 57 mgKOH / g and a number average molecular weight of 4,500 (Mn) per non-volatile content was obtained.

[0318] (Basic dispersion resin (B2-2) solution) In a 500 mL round-bottom four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketene methyltrimethylsilyl acetal as an initiator were added via the addition funnel, and sufficient nitrogen substitution was performed. 0.5 part by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate, which are monomers for block with parent solvent solubility, were added dropwise over 60 minutes using the addition funnel. The reaction flask was cooled in an ice bath to keep the temperature below 40 °C. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, which is a monomer for the colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained THF solution of the block copolymer was reprecipitated in hexane and purified by filtration and vacuum drying. Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottom flask, 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalent to dimethylaminopropyl methacrylamide) as a salt-forming component was added, and the mixture was stirred at a reaction temperature of 30 °C for 20 hours, adjusted by adding PGMAc, and a basic dispersion resin (B2-2) solution with a non-volatile content of 30% was obtained.

[0319] <Production of polymerizable compound (C)> (Polymerizable compound (C-3) having a urethane bond) Into a five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged, the temperature was raised to 70 °C, and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and by IR at 2180 cm ー1The disappearance of the absorption of the isocyanate was confirmed. Subsequently, 35 parts of mercaptoacetic acid and 0.6 part of 4-methoxyphenol were charged, and the mixture was reacted at a temperature of 50 to 60 °C for 6 hours. It was adjusted so that the nonvolatile content became 50% by mass, and a polymerizable compound (C-3) having a urethane bond was obtained.

[0320] <Production of Binder Resin (E)> (Binder Resin (E-1) Solution) 100 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 20% by mass to prepare a binder resin (E-1) solution. The weight average molecular weight (Mw) was 26,000.

[0321] (Binder Resin (E-2) Solution) 100 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube and a stirrer, heated to 80 °C, and after purging the inside of the reaction vessel with nitrogen, 20 parts of methacrylic acid, 20 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile were added dropwise from the dropping tube over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped and dry air was injected for 1 hour while stirring, and then cooled to room temperature. Then, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 °C over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20% by mass to prepare a binder resin (E-2) solution. The weight average molecular weight (Mw) was 18,000.

[0322] (Binder resin (E-3) solution) 200 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, heated to 80 °C, and after purging the inside of the flask with nitrogen, 18 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile were dropped from the dropping tube over 2 hours. After the dropping, the reaction was further carried out at 100 °C for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 20 parts of cyclohexanone was added, and the reaction was continued at 100 °C for 1 hour. Next, the inside of the container was purged with air, 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 part of tris(dimethylamino)phenol, and 0.1 part of hydroquinone were charged into the above container, and the reaction was continued at 120 °C for 6 hours until the non-volatile acid value reached 0.5, and then the reaction was terminated. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 part of triethylamine were added and reacted at 120 °C for 3.5 hours to obtain a resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 °C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to prepare a binder resin (E-3) solution. The weight average molecular weight (Mw) was 19,000.

[0323] (Binder resin (E-4) solution) A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2’-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butyl peroxy 2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation), and 40 parts of PGMAc were well stirred and mixed to prepare a mixture. As a chain transfer agent dropping tank, 8 parts of n-dodecanethiol and 32 parts of PGMAc were well stirred and mixed to prepare a mixture. 200 parts of PGMAc were charged into the reaction vessel, and after nitrogen substitution, the mixture was heated in an oil bath with stirring until the temperature of the reaction vessel reached 90 °C. After the temperature of the reaction vessel stabilized at 90 °C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while maintaining the temperature at 90 °C. Sixty minutes after the dropping was completed, heating was started to raise the temperature of the reaction vessel to 110 °C. After maintaining at 110 °C for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of an oxygen / nitrogen = 5 / 95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110 °C for 12 hours as it was. Thereafter, 150 parts of PGMAc were added and cooled to room temperature. Approximately 2 g of the resin solution was sampled and dried by heating at 180 °C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to obtain a binder resin (E-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile content was 2 mg KOH / g.

[0324] (Binder resin (E-5) solution) 150 parts of PGMAc were introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube. After changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 °C. Then, a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued at 100 °C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts [0.5 mol, (100 mol% with respect to the glycidyl groups of the glycidyl methacrylate used in this reaction)] of methacrylic acid, 0.9 part of tris(dimethylaminomethyl)phenol, and 0.145 part of hydroquinone were introduced into the flask. The reaction was continued at 110 °C for 6 hours, and the reaction was terminated when the nonvolatile acid value reached 1 mg KOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added, and the mixture was reacted at 120 °C for 3.5 hours to obtain a resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 20% by mass to prepare a binder resin (E-5) solution. The weight average molecular weight (Mw) was 12,000.

[0325] (Binder resin (E-6) solution) Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 150 parts of PGMAc was introduced. After changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 °C. Then, a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 136 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued at 100 °C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)] of glycidyl methacrylate, 0.9 part of tris(dimethylaminomethyl)phenol, and 0.145 part of hydroquinone were added to the flask, and the reaction was continued at 110 °C for 6 hours to obtain a resin solution with an acid value of 79 mgKOH / g. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 °C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to prepare a binder resin (E-6) solution. The weight average molecular weight (Mw) was 13,000.

[0326] <Production of Dispersion> (Dispersion 1) Using zirconia beads with a diameter of 0.5 mm, dispersion was carried out with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 3 hours, followed by filtration through a filter with a pore size of 1.0 μm to prepare Dispersion 1 with the following composition. The organic solvent (Q-1) is PGMAc. Fine-particle pigment (A1-1): 14.0 parts by mass Solution of dispersion resin (B1-1) having an acidic group: 10.0 parts by mass Solution of dispersion resin (B1-1-2) having an acidic group: 10.0 parts by mass Dye derivative (G-1): 2.0 parts by mass Organic solvent (Q-1): 64.0 parts by mass

[0327] Dye derivative (G-1): The following structure

Chemical formula

[0328] Dispersions 2 to 9 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts described in Table 1 were changed.

[0329]

Table 1

[0330] Dye derivative (G-2) in Table 1: The following structure

Chemical formula

[0331] <Production of photosensitive composition> [Example 1] (Photosensitive composition 1) While blowing dry nitrogen gas into a container, the following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive composition 1. Dispersion 1: 17.0 parts by mass Dispersion 2: 15.0 parts by mass Dispersion 3: 0.3 parts by mass Polymerizable compound (C-1): 3.0 parts by mass Polymerizable compound (C-2): 2.0 parts by mass Polymerizable compound (C-3): 2.0 parts by mass Compound (D1-1) represented by the general formula (1): 0.7 parts by mass Photoinitiator (D2-1): 0.7 parts by mass Binder resin (E) solution: 10.0 parts by mass Sensitizer (F1-1): 0.5 parts by mass Thermosetting compound (I): 0.3 parts by mass Thiol-based chain transfer agent (J): 0.3 parts by mass Polymerization inhibitor (K): 0.1 parts by mass Antioxidant (M): 0.1 parts by mass Leveling agent (M): 1.0 parts by mass Organic solvent (Q): 46.9 parts by mass

[0332] For the obtained photosensitive composition 1, the contents of specific metal elements and the content of water were measured.

[0333] [Examples 2 to 22, Comparative Examples 1 to 3] (Photosensitive compositions 2 to 25) The photosensitive composition 1 of Example 1 was used to prepare photosensitive compositions 2 to 21 and Examples 23 to 25 in the same manner as in Example 1, except that the raw materials and amounts described in Tables 2-1 to 2-3 were changed. For the photosensitive composition 22, it was prepared with the same composition as the photosensitive composition 1 of Example 1, except that dry nitrogen gas was not blown in.

[0334] [Table 2-1]

[0335] [Table 2-2]

[0336] [Table 2-3]

[0337] For each of the raw materials described in Tables 2-1 to 2-3, it is as follows.

[0338] [Polymerizable compound (C)] C-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.) C-2: Aronix M-520 (manufactured by Toagosei Co., Ltd.) C-3: The polymerizable compound (C-3) having the above urethane bond C-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

[0339] [Photoinitiator (D)] (Compound (D1) represented by general formula (1)) D1-1: Compound of the above chemical formula (2) D1-2: Compound of the above chemical formula (3) D1-3: Compound of the above chemical formula (4)

[0340] (Photoinitiator (D2) other than the compound (D1) represented by general formula (1)) D2-1: Omnirad 907 (manufactured by IGM Resins, alkylphenone compound) D2-2: Omnirad 369 (manufactured by IGM Resins, alkylphenone compound) D2-3: Omnirad 379 (manufactured by IGM Resins, alkylphenone compound) D2-4: Omnirad TPO (manufactured by IGM Resins, acylphosphine oxide compound) D2-5: B-CIM (manufactured by Hodogaya Chemical Co., Ltd., biimidazole compound) D2-6: IRGACURE OXE-01 (manufactured by BASF Japan, oxime compound)

[0341] [Binder resin (E) solution] Solutions of binder resins (E-1) to (E-6) were each mixed in the same amount to obtain a binder resin (E) solution.

[0342] [Sensitizer (F)] (Thioxanthone-based compound (F1)) F1-1: 2,4-Diethylthioxanthone (Benzophenone-based compound (F2)) F2-1: 4,4’-Bis(diethylamino)benzophenone

[0343] [Thermosetting compound (I)] (Epoxy compound (I1)) I1-1: EHPE-3150 (manufactured by Daicel) I1-2: Denacol EX611 (manufactured by Nagase ChemteX) I1-3: Triglycidyl isocyanurate The above (I1-1) to (I1-3) were each mixed in the same amount to obtain a thermosetting compound (I).

[0344] [Thiol-based chain transfer agent (J)] J-1: Trimethylolethane tris(3-mercaptobutyrate) J-2: Trimethylolpropane tris(3-mercaptobutyrate) J-3: Pentaerythritol tetrakis(3-mercaptopropionate) J-4: Trimethylolpropane tris(3-mercaptopropionate) J-5: Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate The above (J-1) to (J-5) were each mixed in the same amount to obtain a thiol-based chain transfer agent (J).

[0345] [Polymerization inhibitor (K)] K-1: 4-Methylcatechol K-2: Methylhydroquinone K-3: t-Butylhydroquinone The above (K-1) to (K-3) were each mixed in the same amount to obtain a polymerization inhibitor (K).

[0346] [UV absorber (L)] L-1: TINUVIN 400 (manufactured by BASF Japan Ltd.) L-2: TINUVIN 900 (manufactured by BASF Japan Ltd.) The above (L-1) and (L-2) were each mixed in the same amount to obtain a UV absorber (L).

[0347] [Antioxidant (M)] M-1: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate M-2: Dioctadecyl 3,3'-thiodipropionate M-3: Tris[2,4-di-(t)-butylphenyl]phosphine M-4: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate M-5: p-Octylphenyl salicylate The above (M-1) to (M-5) were each mixed in the same amount to obtain the antioxidant (M).

[0348] [Leveling agent (N)] N-1: BYK-330 (manufactured by BYK-Chemie GmbH) N-2: Megafac F-551 (manufactured by DIC Corporation) The above (N-1) and (N-2) were each mixed in an amount of 1 part and dissolved in 98 parts of PGMAc to obtain a mixed solution as the leveling agent (N).

[0349] [Organic solvent (Q)] Q-1: 30 parts of propylene glycol monomethyl ether acetate Q-2: 30 parts of cyclohexanone Q-3: 10 parts of ethyl 3-ethoxypropionate Q-4: 10 parts of propylene glycol monomethyl ether Q-5: 10 parts of cyclohexanol acetate Q-6: 10 parts of dipropylene glycol methyl ether acetate The above (Q-1) to (Q-6) were each mixed in the above parts by mass to obtain the organic solvent (Q).

[0350] [Evaluation of photosensitive composition] The following evaluations were performed on the obtained photosensitive compositions 1 to 25 (Examples 1 to 22, Comparative Examples 1 to 3). The evaluation results are shown in Table 3.

[0351] [Evaluation of storage stability (1): Viscosity] The obtained photosensitive composition was placed in a sealed container and stored at 40 °C for 1 week. The change rate of viscosity before and after storage was calculated by the following formula and evaluated. The viscosity was measured at 25 °C under the condition of a rotation speed of 50 rpm using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "ELD-type viscometer"). A value of 2 or more is practical. [Viscosity change rate over time]=|([Initial viscosity]-[Viscosity over time]) / [Initial viscosity]|×100 3: Those with a change rate of less than 5% 2: Those with a change rate of 5% or more and less than 10% 1: Those with a change rate of 10% or more

[0352] [Storage stability evaluation (2): Sensitivity] The obtained photosensitive composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness became 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Then, after cooling this substrate to room temperature, ultraviolet exposure was performed using a high-pressure mercury lamp through a photomask under the conditions of illuminance of 30 mW / cm 2 , 50 mJ / cm 2 . After that, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 °C, washed with ion-exchanged water, air-dried, and then post-baked at 230 °C for 20 minutes in a clean oven to form an initial pattern on the substrate. Regarding the formed pattern, the width of the pattern was measured using a scanning electron microscope, and this was taken as the initial pattern width. Thereafter, the photosensitive composition was placed in a sealed container and stored at 40 °C for 1 week, and a pattern after storage was created under the same conditions as the formation of the initial pattern for the photosensitive composition after storage. Regarding the formed pattern after storage, the width of the pattern was measured using a scanning electron microscope and evaluated according to the following criteria. 2 or more is practical. 3: The pattern width after storage is in the range of 95% or more and 105% or less of the initial pattern width 2: The pattern width after storage is 90% or more and less than 95% of the initial pattern width, or in the range of exceeding 105% and 110% or less 1: The pattern width after storage is less than 90% of the initial pattern width or exceeds 110%

[0353] [Development residue evaluation] The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm × width of 100 mm and a thickness of 0.7 mm using a spin coater so that the dry film thickness became 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Then, using an ultra-high pressure mercury lamp, illuminance 30 mW / cm 2, 50 mJ / cm 2 at 50 mJ / cm 2 , ultraviolet light was irradiated through a photomask with a 100-μm-wide stripe pattern. Further, after cooling this substrate to room temperature, it was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, and air-dried. The obtained substrate was post-baked in a clean oven at 230°C for 20 minutes to form a stripe-shaped pattern on the substrate. The pattern was observed with an optical microscope, and the amount of residue remaining in the unexposed area was evaluated by binarization processing of the image. The evaluation criteria are as follows, and 2 or more is practical. 3: Development residue is less than 1.5% of the unexposed area 2: Development residue is 1.5% or more and less than 3% of the unexposed area 1: Development residue is 3% or more of the unexposed area

[0354] [Pattern Shape Evaluation] The obtained photosensitive composition was applied by spin coating method onto a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, it was irradiated at illuminance of 30 mW / cm 2 , 50 mJ / cm 2 through a photomask with a stripe pattern with a pitch of 5 μm. Then, this substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 230°C for 20 minutes to obtain a substrate for evaluation. The obtained substrate was evaluated by measuring the maximum and minimum line widths of 10 stripe patterns using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon and obtaining their average. The evaluation criteria are as follows, and 2 or more is practical. 3: The difference between the maximum and minimum line widths is less than 1.0 μm 2: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm 1: The difference between the maximum and minimum line widths is 1.5 μm or more

[0355] [Solvent Resistance Evaluation] For the obtained photosensitive composition, it was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a size of 100 mm in length × 100 mm in width and 0.7 mm thickness by spin coating method so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, the illuminance was 30 mW / cm 2 , 50 mJ / cm 2 , and exposure was performed through a photomask with a 100-μm-wide stripe pattern. Then, this substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 °C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 230 °C for 20 minutes. After that, after cooling this substrate to room temperature, the substrate was immersed in N-methylpyrrolidone at room temperature for 30 minutes, washed with ion-exchanged water, air-dried, and the 100-μm-wide stripe pattern part was observed using an optical microscope. The evaluation criteria are shown below. Two or more are practical. 3: No change in appearance or color. 2: Some wrinkles occur, but there is no change in color. 1: Peeling or fading occurs.

[0356] [Foreign Substance Evaluation] The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a size of 100 mm in length × 100 mm in width and 0.7 mm thickness by spin coating method so that the dry film thickness was 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, ultraviolet exposure was performed using a high-pressure mercury lamp through a photomask under the conditions of illuminance 30 mW / cm 2 , 50 mJ / cm 2 . Then, this substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 °C, washed with ion-exchanged water and air-dried, and post-baked in a clean oven at 230 °C for 20 minutes. After that, the substrate was cooled at room temperature, and the number of foreign substances on the pattern and between the patterns was measured. The evaluation was performed by surface observation using a metallurgical microscope "BX60" (manufactured by Olympus Corporation). The magnification was set to 500 times, and the number of foreign substances observable in any 5 fields of view by transmission was measured by integration. The evaluation criteria are as follows, and 2 or more is practical. 3: The number of foreign substances is less than 10 2: The number of foreign substances is 10 or more and less than 20 1: The number of foreign substances is 20 or more

[0357]

Table 3

Claims

1. A photosensitive composition comprising a pigment (A), a dispersion resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a binder resin (E), wherein the dispersion resin (B) includes a dispersion resin (B1) having an acidic group with an acid value of 30 to 250 mgKOH / g, the photopolymerization initiator (D) includes a compound (D1) represented by the following general formula (1) and a photopolymerization initiator (D2) other than the compound (D1) represented by the following general formula (1), and the photopolymerization initiator (D) is a photosensitive composition substantially free of an oxime compound. General formula (1) 【Chemical 1】 (In general formula (1), R １ , R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ３ represents a hydrogen atom or a monovalent substituent.)

2. The photosensitive composition according to claim 1, wherein the photopolymerization initiator (D2) is at least one selected from the group consisting of an alkylphenone compound, an acylphosphine oxide compound, and a biimidazole compound.

3. The photosensitive composition according to claim 1 or 2, wherein the polymerizable compound (C) includes a lactone-modified polymerizable compound and / or a polymerizable compound having a urethane bond.

4. The dispersion resin (B1) having an acidic group with an acid value of 30 to 250 mgKOH / g includes a polyester moiety having a carboxyl group formed by reacting an acid anhydride group in at least one acid anhydride selected from the group consisting of tetracarboxylic dianhydrides and tricarboxylic anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer moiety formed by radical polymerization of a monomer, and the photosensitive composition according to any one of claims 1 to 3 includes the dispersion resin (B1-1).

5. The photosensitive composition according to any one of claims 1 to 4, further comprising a sensitizer (F).

6. An optical filter having a substrate and a filter segment formed from the photosensitive composition according to any one of claims 1 to 5.

7. An image display device having the optical filter according to claim 6.

8. A solid-state imaging device having the optical filter according to claim 6.

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