Color filter photosensitive composition, color filter, image display device, and solid-state image sensor

Abstract

To provide a photosensitive composition capable of forming a coating film that is superior in terms of a line width of a formed pattern, adhesion, and chemical resistance even if a low-temperature heating step is employed.SOLUTION: A photosensitive composition is provided, comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), where the polymerization initiator (D) is a triazine peroxide represented by a formula below or another specific formula.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photosensitive composition used for forming a color filter or the like.

Background Art

[0002] Due to the spread of liquid crystal display devices, digital cameras, smartphones, infrared sensors, etc., the demand for optical filters used in these devices is increasing. And, for the purpose of making these devices lightweight, thin, and power-saving, organic EL (Electro-Luminescence) display devices using OLED (Organic Light Emitting Diode) or the like that do not require a backlight, and the use of organic materials for the optoelectronic conversion film in image sensors are being studied.

[0003] Since the heat resistance of the organic light-emitting layer used in organic EL display devices and the like is generally low, it is preferable that the photosensitive composition for forming a color filter used in organic EL display devices performs the heating process at a low temperature, for example, 150 ° C or lower. Therefore, Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble resin having an alkoxysilyl group.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the conventional photosensitive composition did not have satisfactory levels of line width, adhesion, and chemical resistance of the pattern formed in the heating process at 120 ° C or lower.

[0006] An object of the present invention is to provide a photosensitive composition for a color filter capable of forming a film having excellent line width, adhesion, and chemical resistance of a pattern formed even at a low temperature in a heating step.

Means for Solving the Problems

[0007] <1>The photosensitive composition for a color filter of the present invention contains a dye (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an acidic resin type dispersant (S). The polymerization initiator (D) contains one or more of a triazine peroxide (D1a) represented by the following general formula (1a) and a triazine peroxide (D1b) represented by the following general formula (1b). General formula (1a)

Chemical formula

[0008] In general formula (1a), R 1 and R 3 each independently represent a methyl group or an ethyl group. R 2 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. X is an aromatic ring-containing group, and n represents an integer from 0 to 2. General formula (1b)

Chemical formula

[0009] In general formula (1b), R 1 and R 2 each independently represent a methyl group or an ethyl group, R 3 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, and R 4 represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -Y-R, or -N-RR', where Y is an oxygen atom or represents a sulfur atom, and R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 2 carbon atoms 0, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. X represents an aromatic ring-containing group. <2>The photosensitive composition for a color filter according to <1>, which contains a thermosetting compound (E). <3>The polymerization initiator (D) further contains an oxime ester-based initiator (D2), and the photosensitive composition for a color filter according to <1> or <2>. <4>A color filter comprising a substrate and a film formed from the photosensitive composition for a color filter according to any one of <1> to <3>. <5>An image display device having the color filter according to <4>. <6>A solid-state imaging device having the color filter according to <5>.

Advantages of the Invention

[0010] According to the present invention described above, even when the heating step is at a low temperature, a photosensitive composition for a color filter capable of forming a film excellent in the line width, adhesion, and chemical resistance of the pattern to be formed can be provided. Further, the present invention can provide a color filter, an image display device, and a solid-state imaging device.

Brief Description of the Drawings

[0011]

Figure 1

Modes for Carrying Out the Invention

[0012] The terms used in this specification are defined below. When expressed as “(meth)acryloyl,” “(meth)acryl,” “(meth)acrylic acid,” “(meth)acrylate,” or “(meth)acrylamide,” unless otherwise specified, they represent “acryloyl and / or methacryloyl,” “acryl and / or methacryl,” “acrylic acid and / or methacrylic acid,” “acrylate and / or methacrylate,” or “acrylamide and / or methacrylamide,” respectively. “C.I.” means Color Index (C.I.). The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group. A monomer is in the state before polymerization. A monomer unit is in the state that constitutes the resin after polymerization.

[0013] The photosensitive composition for a color filter of the present invention (hereinafter also referred to as the photosensitive composition) is a photosensitive composition containing a dye (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an acidic resin type dispersant (S), wherein the polymerization initiator (D) contains one or more of a triazine peroxide (D1a) represented by the general formula (1a) and a triazine peroxide (D1b) represented by the general formula (1b). The photosensitive composition of the present invention is used by forming a film. The film is preferably used for a color filter.

[0014] The film formed from the photosensitive composition of the present invention contains a triazine peroxide (D1a) represented by the general formula (1a) or a triazine peroxide (D1b) represented by the following general formula (1b), and thus has a photopolymerizability capable of efficiently absorbing light such as light with a wavelength of 365 nm and generating radicals during exposure. Further, since it also has a thermal polymerizability capable of generating radicals by heat, the film is cured even at a low temperature in the heating step. As a result, when forming a pattern by the photolithography method, the line width of the pattern is less likely to become thick, and it is easy to form a high-definition pattern. Furthermore, a film with good pattern adhesion and excellent chemical resistance can be formed.

[0015] <Dye (A)> The coloring agent (A) includes pigments, dyes, and near-infrared absorbing pigments. Pigments include inorganic pigments and organic pigments. Red pigments include, for example, 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, etc.

[0016] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 7 3, etc.

[0017] Yellow pigments include, for example, 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, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233 are preferred.

[0018] Green pigments include, for example, 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. Among these, C.I. Pigment Green 7, 36, 58, 59, 62, 63 are preferred.

[0019] Blue pigments include, for example, 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. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16 are preferred.

[0020] Examples of the purple pigment include 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. Among these, C.I. Pigment Violet 19 and 23 are preferred.

[0021] Examples of the black pigment include C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc.

[0022] Furthermore, examples of inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, cobalt blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc.

[0023] The near-infrared absorbing dye is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm. Examples of the near-infrared absorbing dye include pigments (also referred to as near-infrared absorbing pigments) and dyes (also referred to as near-infrared absorbing dyes). In addition, a near-infrared absorbing pigment and a near-infrared absorbing dye may be used in combination. From the viewpoint of heat resistance, a near-infrared absorbing pigment is preferred. The solubility of the near-infrared absorbing pigment in 100 g of propylene glycol monomethyl ether acetate at 25 °C is preferably less than 2 g, more preferably less than 1 g, and even more preferably 0.5 g or less.

[0024] Examples of the near-infrared absorbing dye include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, etc. Among these also, from the viewpoint of heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, and squarylium compounds are preferred, and naphthalocyanine compounds and squarylium compounds are more preferred.

[0025] (Squarylium compound)

[0026] Specific examples of squarylium compounds are shown below. However, the present invention is not limited thereto.

Chemical formula

[0027]

Chemical formula

[0028] (Pyrrolopyrrole compound) As the pyrrolopyrrole compound, a compound represented by the following general formula (5) is preferable.

[0029] General formula (5)

Chemical formula

[0030] (In general formula (5), R 1X and R 1Y each independently represent an alkyl group, an aryl group, or a heteroaryl group, R 2 and R 3 each independently represent a hydrogen atom or a substituent, R 2 and R 3 may be bonded to each other to form a ring, R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4X R 4Y or a metal atom, and R 4 is R 1X 、R 1Y and R 3 and may be covalently or coordinately bonded to at least one selected from the group consisting of. R 4X R 4Y each independently represent a substituent. The compound represented by general formula (5) is described in JP-A-2009-263614, JP-A-2011-68731, and WO 2015 / 166873.

[0031] Specific examples of the pyrrolopyrrole compound are shown below. In the following structural formulas, ME represents a methyl group and PH represents a phenyl group. Note that the present invention is not limited thereto.

[0032]

Chemical formula

[0033] (Naphthalocyanine compound) As the naphthalocyanine compound, a compound represented by the following general formula (6) is preferable.

[0034] General formula (6)

Chemical formula

[0035] In general formula (6), R 1 to R 24 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, -OR 25 or -SR 26 , and R 25 and R 26 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

[0036] Examples of the halogen atom represented by R 1 to R 24 in general formula (6) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0037] In general formula (6), M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. When M represents two hydrogen atoms, a structure in which the N-M-N part in general formula (6) is shown as two N-H is formed. Examples of the metal atom represented by M in general formula (6) include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide represented by M in general formula (6) include titanyl and vanadyl. Examples of the metal halide represented by M in general formula (6) include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride, and silicon chloride. As M in general formula (6), copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, or tin(II) chloride is preferable, copper, zinc, vanadyl, or titanyl is more preferable, and vanadyl is particularly preferable.

[0038] Specific examples of the compound represented by general formula (6) are shown below, but the present invention is not limited thereto.

Chemical formula

Chemical formula

Chemical formula

[0039] The naphthalocyanine compound represented by general formula (6) can be used alone or in combination of two or more.

[0040] As the naphthalocyanine compound represented by general formula (6), those having a maximum absorption wavelength in the wavelength range of 750 to 1500 nm are preferable, and those having a maximum absorption wavelength in the wavelength range of 780 to 1000 nm are more preferable.

[0041] Further, the naphthalocyanine compound is preferably a compound represented by the following general formula (7).

[0042] General formula (7)

Chemical formula

[0043] In general formula (7), R 1 ~R 24 each independently represents a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, or a sulfamoyl group which may have a substituent. Z is a polymer moiety containing a monomer unit represented by general formula (8) or a phosphorus compound moiety represented by general formula (9).

[0044]

Chemical formula

[0045] In general formula (8), X is -CONH-R 25 -, -COO-R 26 -, -CONH-R 27 -O-, -COO-R 28 -O-, R 25 ~R 28 represents an alkylene group or an arylene group in which carbon atoms are connected to each other by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. R 31 represents hydrogen or a methyl group. n is an integer of 0 or 1 to 10. * is a bond to Al. In general formula (9), R 29 and R 30each independently represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R 29 and R 30 may be bonded to each other to form a ring. * represents a bond to Al.

[0046] Specific examples of the compound represented by the general formula (7) are shown below. Note that the present invention is not limited thereto.

[0047]

Chemical formula

Chemical formula

[0048] The near-infrared absorbing dye can be used alone or in combination of two or more. When using two or more in combination, it is preferable to use compounds having different maximum absorption wavelengths. Thereby, compared with the case of using one kind of near-infrared absorbing dye, the waveform of the absorption spectrum spreads, and near-infrared rays in a wide wavelength range can be absorbed.

[0049] (Dye) Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Further, as the dye, derivatives thereof, or lake pigments obtained by lake-forming the dye can also be used.

[0050] Acid dyes preferably have acidic groups such as sulfonic acid and carboxylic acid. Direct dyes preferably form salt compounds with inorganic salts of acid dyes, or with nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds. Further, salt compounds that are salts of resin components having these functional groups and acid dyes are also preferred. Also, salt compounds can be easily converted into photosensitive compositions excellent in resistance (light resistance, solvent resistance) by sulfonamidation to be modified into sulfonic acid amide compounds. In addition, salt compounds of acid dyes and compounds having an onium base are also preferred because they are excellent in resistance (light resistance, solvent resistance). Note that as the compound having an onium base, a resin having a cationic group is preferred.

[0051] Basic dyes can be used as they are, but salt compounds formed by salification with organic acids, perchloric acid, or metal salts thereof are preferred. Salt compounds of basic dyes are preferred because they are excellent in resistance (light resistance, solvent resistance) and affinity with pigments. Also, as the anion component acting as a counterion in the salt compound of the basic dye, an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, and a salt compound formed by salifying with an acid dye are preferred. Note that the resistance is further improved when the salt compound contains a polymerizable unsaturated group in the molecule.

[0052] The chemical structure of the dye is preferably a pigment structure derived from a pigment selected from, for example, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0053] The coloring agent (A) can be used alone or in combination of two or more kinds.

[0054] The content of the coloring agent (A) is preferably 0.5 to 80% by mass, more preferably 1 to 60% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

[0055] (Micronization of organic pigments) The organic pigment is preferably used after being micronized. The micronization method is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation methods can be used. Among these, salt milling treatment by the kneader method, which is a type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the micronized 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.

[0056] For the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment is coated with the resin, and the stability, light resistance, etc. are improved. 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, those that are solid at room temperature, preferably water-insoluble, and partially soluble in the above organic solvent are preferable. The addition amount of the resin is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[0057] <Alkali-soluble resin (B)> The alkali-soluble resin (B) is not particularly limited as long as it can be dissolved in an alkali developer. The alkali-soluble resin (B) can be classified into an alkali-soluble resin containing a polymerizable unsaturated group and an alkali-soluble resin not containing a polymerizable unsaturated group. And the alkali-soluble groups possessed by the alkali-soluble resin (B) include, for example, carboxyl group, phosphate group, sulfonic acid group, hydroxyl group, phenolic hydroxyl group, etc. Among these, the carboxyl group is preferable. The alkali-soluble resin is preferably a chain-like random polymer. The chain includes branched chains.

[0058] Examples of the resin species of the alkali-soluble resin (B) include acrylic resins having an acidic group, α-olefin / (anhydrous) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydrous) maleic acid copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of developability, heat resistance, and transparency, and acrylic resins having an acidic group are more preferred.

[0059] [Alkali-soluble resin (B1) containing a polymerizable unsaturated group] The alkali-soluble resin (B1) containing a polymerizable unsaturated group is a resin obtained by imparting a polymerizable unsaturated group to the above alkali-soluble resin (B). In this specification, the alkali-soluble resin containing a polymerizable unsaturated group is preferably a resin synthesized by the following methods (i) and (ii). Thereby, the crosslinking density of the film formed from the photosensitive coloring composition by light irradiation is further improved, and the chemical resistance in low-temperature curing is improved.

[0060] [Method (i)] Method (i) is, for example, first, synthesizing a polymer of an epoxy group-containing monomer and other monomers. 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 an alkali-soluble resin (B1) containing a polymerizable unsaturated group.

[0061] Examples of the epoxy group-containing monomer include 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.

[0062] Other monomers include, for example, (meth)acrylates such as 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, or ethoxypolyethylene glycol (meth)acrylate, or (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, fatty acid vinyls such as vinyl acetate or vinyl propionate, and the like.

[0063] Also, cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-male N-substituted maleimides such as (midophenyl)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-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimidehexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, etc.; EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc. Also included are phosphate ester group-containing monomers obtained by reacting a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl groups of hydroxyl group-containing monomers.

[0064] Examples of the monocarboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, cyano-substituted products of (meth)acrylic acid, etc.

[0065] Examples of the polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. Note that the polybasic acid anhydrides may have a carboxyl group that does not form an acid anhydride.

[0066] Also, as a method similar to method (i), for example, a polymer of a monocarboxyl 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 an alkali-soluble resin (B1) containing a polymerizable unsaturated group.

[0067] [Method (ii)] Method (ii) includes, for example, synthesizing a polymer by synthesizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Next, a method of synthesizing a resin by reacting the isocyanate group of an isocyanate group-containing monomer with the hydroxyl group of the polymer is exemplified.

[0068] 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. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0069] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis〔methacryloyloxy〕ethyl isocyanate.

[0070] Examples of monomers that can be used in addition to the above monomers include the other monomers exemplified in the above method (i).

[0071] [Alkali-soluble resin (B2) that does not contain a polymerizable unsaturated group] The alkali-soluble resin (B2) that does not contain a polymerizable unsaturated group can contain a reactive group other than the polymerizable unsaturated group.

[0072] [Alkali-soluble resin (B2-1) containing a blocked isocyanate group]

[0073] The alkali-soluble resin (B) can contain a blocked isocyanate group. A resin containing a blocked isocyanate group is excellent in low-temperature curability and has improved chemical resistance.

[0074] The alkali-soluble resin (B2-1) containing a blocked isocyanate group has a monomer unit containing a blocked isocyanate group. The blocked isocyanate group is a group in which an isocyanate group is protected with a compound that dissociates by heat (hereinafter also referred to as a blocking agent). The dissociation temperature of the blocking agent is preferably 70 to 150°C, more preferably 80 to 135°C. The monomer unit containing a blocked isocyanate group can protect the isocyanate group with a blocking agent after polymerization of the monomer containing a blocked isocyanate group. Or it may be polymerized after protecting the isocyanate group of the monomer containing a blocked isocyanate group.

[0075] Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, and the like. Also, an equimolar reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0076] The blocking agent preferably comprises one or more selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. From the viewpoints of the protection reaction and the deprotection reaction, one or more selected from the group consisting of an oxime compound, a phenol compound, an active methylene compound, and a pyrazole compound are more preferable.

[0077] Examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and the like. Among these, methyl ethyl ketone oxime is preferable. oxime is preferred. Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, and the like. Examples of the phenol compound include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, and the like. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferable. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, carbazole, and the like. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, and the like. Among these, diethyl malonate is preferable. Examples of the pyrazole compound include pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc. Among these, 3,5-dimethylpyrazole is preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, etc. Examples of the imide compound include succinimide, maleimide, maleic imide, phthalimide, etc. Examples of the urea compound include urea, thiourea, ethylene urea, etc. Examples of the imine compound include ethylene imine, polyethylene imine, etc. Examples of the bisulfite compound include sodium bisulfite, potassium bisulfite, etc.

[0078] The blocking agent can be used alone or in combination of two or more.

[0079] Examples of the blocked isocyanate group-containing monomer include, for example, the following compounds. However, the present invention is not limited thereto.

[0080]

Chemical formula

[0081] Examples of the commercially available blocked isocyanate group-containing monomer include Karens MOI-DEM (desorption temperature of the blocking agent: 85 - 95 °C), MOI-BP (desorption temperature of the blocking agent: 105 - 115 °C), MOI-BM (125 - 135 °C), etc. manufactured by Showa Denko KK.

[0082] The content of the monomer unit containing a blocked isocyanate group is preferably 1 to 50 mol%, more preferably 5 to 40 mol% in all the constituent units of the alkali-soluble resin (B) from the viewpoints of storage stability and chemical resistance in low-temperature curing.

[0083] The weight-average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 25,000. Also, the value of Mw / Mn (number-average molecular weight) is preferably 10 or less.

[0084] The acid value of the alkali-soluble resin (B) is preferably 20 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g.

[0085] The alkali-soluble resin (B) can be used alone or in combination of two or more.

[0086] The content of the alkali-soluble resin (B) is preferably 20 to 400 parts by mass, more preferably 30 to 250 parts by mass with respect to 100 parts by mass of the dye (A).

[0087] <Polymerizable compound (C)> Examples of the polymerizable compound (C) include monomers or oligomers having a polymerizable unsaturated group. The polymerizable compound (C) includes, for example, polymerizable compounds having an acid group, polymerizable compounds having a urethane bond, and other polymerizable compounds.

[0088] (Polymerizable compound having an acid group) When the photosensitive composition of the present invention contains a polymerizable compound having an acid group, the solubility of the coating film in an alkali developer during alkali development is improved, so that the development rate is improved and residues can be suppressed. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphate group.

[0089] Polymerizable compounds having an acid group include, for example, esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates with (meth)acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates, etc. For example, free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligo(meth)acrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid, etc.; free carboxyl group-containing oligoesters of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, etc. with monohydroxy monoacrylates or monohydroxy mono(meth)acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.

[0090] Commercially available products include Biscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, etc. manufactured by Toagosei Co., Ltd.

[0091] (Polymerizable compound having a urethane bond) The photosensitive coloring composition of the present invention can suppress the precipitation of color materials when the coating film is heated by containing a photopolymerizable compound having a urethane bond. In addition, chemical resistance and adhesion to the substrate can be improved.

[0092] Polymeric compounds having urethane bonds include, for example, polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting with a (meth)acrylate having a hydroxyl group, and the like.

[0093] (Meth)acrylates 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.

[0094] Also, polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0095] Commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

[0096] Other polymerizable compounds include, 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)acrylate of methylolated melamine, epoxy (meth)acrylate, urethane acrylate and other various acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like.

[0097] Commercially available products include KAYARAD R-128H, R526, and PEG400DA manufactured by Nippon Kayaku Co., Ltd. , 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, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and 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., NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., etc. may be mentioned.

[0098] The polymerizable compound can be used alone or in combination of two or more.

[0099] The compounding amount of the polymerizable compound (C) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0100] [Polymerization initiator (D)] The polymerization initiator (D) contains triazine peroxide (D1). The triazine peroxide (D1) contains one or more of triazine peroxide (D1a) represented by the general formula (1a) and triazine peroxide (D1b) represented by the general formula (1b). The triazine peroxide (D1a) represented by the general formula (1a) or the triazine peroxide (D1b) represented by the general formula (1b) has both photopolymerizability capable of efficiently absorbing light with a wavelength of 365 nm or the like emitted from a lamp such as a high-pressure mercury lamp or an LED and generating radicals, and thermal polymerizability capable of generating radicals by heat, and can generate radicals even in a low-temperature heating step. Note that the triazine peroxide (D1a) represented by the general formula (1a) and the triazine peroxide (D1b) represented by the general formula (1b) can be used in combination.

[0101] [Triazine peroxide (D1a)] The triazine peroxide (D1a) represented by the general formula (1a) (hereinafter referred to as triazine peroxide (D1a)) is the following compound. General formula (1a)

Chemical formula

[0102] In the general formula (1a), R 1 and R 3 are independently a methyl group or an ethyl group, R 2 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, n represents an integer from 0 to 2, X is an aromatic ring-containing group, and the general formula (2a): Ar 1 , Ar 2 , Ar 3 or Ar 4 The aryl group represented by is preferred.

[0103] In the general formula (1a), R 1 and R 3 independently represent a methyl group or an ethyl group. R 1 and also R 3 are preferably methyl groups from the viewpoint that the decomposition temperature of the triazine peroxide is high and the storage stability of the polymerizable composition is high.

[0104] In the general formula (1a), R 2is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The alkyl group is linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group, and an isopropylphenyl group. Among these, from the viewpoint of easy synthesis of the triazine peroxide, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferable. From the viewpoint that the decomposition temperature of the triazine peroxide is high, resulting in high storage stability of the polymerizable composition and high sensitivity to the light of the lamp, a methyl group and an ethyl group are more preferable.

[0105] In the general formula (1a), n is represented by an integer from 0 to 2. From the viewpoint of easy synthesis of the triazine peroxide, n is preferably 0 or 1. When n is 0, X is Ar 2 , Ar 3 or Ar 4 ; when n is 1, X is Ar 1 which is more preferable from the viewpoint of efficiently absorbing the light of the lamp and reducing the yellowness of the cured product. General formula (2a)

Chemical formula

[0106] In the general formula (2a), m represents an integer from 0 to 3, and R 4 is an independent substituent, which represents an alkyl group having 1 to 18 carbon atoms, a substituent represented by the general formula (3a): R 5 -Y-, a nitro group, or a cyano group, where Y represents an oxygen atom or a sulfur atom, and R 5 is a hydrocarbon group having 1 to 18 carbon atoms which may have an ether bond, a thioether bond, and / or a hydroxyl group at the terminal, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or -CO-R. Alternatively, R 4 is two adjacent substituents of the general formula (3a): R 5-Y- represents a hydrocarbon group that forms a 5- to 6-membered ring. Each R independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms.

[0107] In the general formula (2a), m is represented by an integer from 0 to 3. From the viewpoint of easy synthesis of the triazine peroxide, m is preferably from 0 to 2, and from the viewpoint of efficiently absorbing the light of the lamp, m is more preferably 1.

[0108] Each R 4 is, from the viewpoint of efficiently absorbing the light of the lamp, an independent substituent, an alkyl group having 1 to 8 carbon atoms, or a substituent represented by the general formula (3a): R 5 -Y-, where Y represents an oxygen atom, and R 5 is a hydrocarbon group having 1 to 8 carbon atoms which may have one or more of an ether bond and a hydroxyl group at the terminal in the carbon skeleton, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or R 4 is preferably a hydrocarbon group that forms a 5- to 6-membered ring by two adjacent ones of the general formula (3a): R 5 -X-.

[0109] Each R 4 is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Alkyl groups such as n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, octyl group, 2-ethylhexyl group, dodecyl group, octadecyl group; methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, octyloxy group, 2-ethylhexyloxy group, dodecyloxy group, octadecyloxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-(2-hydroxyethoxy)ethoxy group, 2-(2-ethoxyethoxy)ethoxy group, 3-hydroxy-n-propyloxy group, 3-methoxy-n-propyloxy group, 1,2-dihydroxypropyloxy group, methylenedioxy group, dimethylmethylenedioxy group, ethylenedioxy group and other alkoxy groups; aryloxy groups such as phenyloxy group, 4-isopropylphenyloxy group; alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, hexylsulfanyl group, 2-methoxyethylsulfanyl group, 2-(2-methoxyethoxy)ethylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group, 2-methylphenylsulfanyl group, 4-methylphenylsulfanyl group, acetyl group, n-butanoyl group, 2-ethylhexanoyl group, benzoyl group, 2-methylbenzoyl group and other acyl groups. Compounds represented by the general formula (1a) having these functional groups have a high absorbance at a wavelength of 365 nm and are preferable because they efficiently absorb the light of the lamp.

[0110] Furthermore, among these, from the viewpoints of high solubility in the polymerizable composition of the triazine peroxide (D1a), ease of synthesis, and high sensitivity to the light of the lamp, the R 1 is more preferably a methyl group.

[0111] The R 4 substitution position is not particularly limited. However, when X is Ar 1 in the case of, R 4At least one of them is preferably bonded to the para-position of the triazine group, and when X is Ar 2 in the case of, R 4 at least one of them is preferably bonded to the 4-position of the benzene ring not bonded to the triazine group, and when X is Ar 3 in the case of, the triazine group is preferably bonded to the 1-position of the naphthalene ring, and further R 4 at least one of them is preferably bonded to the 4-position of the naphthalene ring, and when X is Ar 4 in the case of, R 4 at least one of them is preferably bonded to the 4-position of the benzene ring not bonded to the triazine group in order to efficiently absorb the light of the lamp.

[0112] Triazine peroxide (D1a) is exemplified below. However, it is not limited thereto.

Chemical formula

Chemical formula

Chemical formula

[0113] The content of triazine peroxide (D1a) is preferably 0.5 to 7% by mass, more preferably 1 to 3% by mass in the non-volatile content of the photosensitive composition.

[0114] [Triazine peroxide (D1b)] Triazine peroxide (D1b) represented by the general formula (1b) (hereinafter referred to as triazine peroxide (D1b)) is the following compound. General formula (1b)

Chemical formula

[0115] In the general formula (1b), R 1 and R 2 independently represent a methyl group or an ethyl group, R 3 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, and R 4 represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -Y-R, or -N-RR', where Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 2 0 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. X is an aromatic ring-containing group, and the aryl group represented by the following general formula (2b): Ar 1 Ar 2 or Ar 3 is preferred. In the general formula (2b)

Chemical formula

[0116] In the general formula (2b), m represents an integer from 0 to 3, and R 11 are independent substituents, which are an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -Y-R, or -N-RR', where Y and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms.

[0117] In the general formula (1b), R 1 and R 2 independently represent a methyl group or an ethyl group, and from the viewpoint of high decomposition temperature and high storage stability of the polymerizable composition, a methyl group is preferred.

[0118] In general formula (1b), R 3 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The alkyl group may be linear or branched. R 3 is, for example, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group, an isopropylphenyl group, etc. Among these, from the viewpoint of easy synthesis of the triazine peroxide derivative, it is preferably a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, or a phenyl group. Since the decomposition temperature of the triazine peroxide derivative is high, the storage stability of the polymerizable composition is high, and from the viewpoint of high sensitivity to light, a methyl group or an ethyl group is more preferable.

[0119] In general formula (1b), R 4 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -Y-R, or -N-RR', where Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. Since the above R has little influence on the absorption wavelength of the triazine peroxide derivative, good sensitivity can be exhibited even when R 4 is in the above wide range. Further, the "substituent" in the above "optionally substituted" includes a halogen atom, an aliphatic hydrocarbon group which may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, a heterocyclic group-containing group, an acyl group, a cyano group, a nitro group, a carboxyl group, an epoxy group, a hydroxyl group, etc. The above R 4 is, for example, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group, an isopropylphenyl group, etc. Among these, from the viewpoint of easy synthesis of the triazine peroxide derivative, it is preferably a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, or a phenyl group. Since the decomposition temperature of the triazine peroxide derivative is high, the storage stability of the polymerizable composition is high, and from the viewpoint of high sensitivity to light, a methyl group or an ethyl group is more preferable. 4From the perspective of high stability, it is preferably an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, or -Y-R. From the perspective of easy synthesis, it is more preferably -O-R, where R is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms.

[0120] In the general formula (2b), m represents an integer from 0 to 3. From the perspective of easy synthesis, it is preferably that m is from 0 to 2, and from the perspective of efficiently absorbing light, it is more preferably that m is 1.

[0121] In the general formula (2b), R 11 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -Y-R, or -N-RR', where Y is an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. The above R has little influence on the absorption wavelength of the triazine peroxide derivative, so even if R 11 is within the above wide range, good sensitivity is exhibited. Also, the "substituent" in the above "optionally substituted" includes a halogen atom, an aliphatic hydrocarbon group that may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, a heterocyclic group-containing group, an acyl group, a cyano group, a nitro group, a carboxyl group, an epoxy group, a hydroxyl group, etc. The above R 11 is an independent substituent and represents an alkyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (3b): R -Y-, a nitro group, or a cyano group, where the said Y represents an oxygen atom or a sulfur atom, and the said R 11 is an alkyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (3b): R 12 -Y-, a nitro group, or a cyano group, where the said Y represents an oxygen atom or a sulfur atom, and the said R12 has, in the carbon skeleton, an ether bond, a thioether bond, and a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or -CO-R, any one or more of which may have a hydroxyl group at the terminal, and R 11 may form a 5- to 6-membered ring with two adjacent general formulas (3b): R 12 -Y-.

[0122] Specific examples of the triazine peroxide (D1b) of the present invention are shown below, but are not limited thereto.

Chemical formula

[0123] In the present invention, the triazine peroxide (D1b) is preferably compound 19b, compound 23b, compound 25b, compound 26b, compound 27b, compound 31b, compound 32b, compound 33b, compound 35b, compound 37b, compound 38b, compound 39b, compound 43b, compound 44b, compound 45b, compound 46b, compound 47b, compound 48b, compound 49b, compound 50b, compound 51b, compound 52b, compound 53b, compound 54b, compound 55b, compound 56b, compound 57b, compound 60b, compound 61b, compound 73b, compound 77b, compound 78b, compound 79b, compound 81b.

[0124] The content of the triazine peroxide (D1b) is preferably 0.5 to 7% by mass, more preferably 1 to 3% by mass, in the nonvolatile matter of the photosensitive composition.

[0125] [Oxime ester-based initiator (D2)] The polymerization initiator (D) may further contain an oxime ester-based initiator (D2) (hereinafter also referred to as initiator (D2)). By absorbing ultraviolet light, the initiator (D2) causes the cleavage of the N-O bond of the oxime, generating an iminyl radical and an alkoxy radical. These radicals further decompose to generate highly active radicals, enabling the formation of a pattern with a small exposure amount. Therefore, even when the pigment concentration of the photosensitive coloring composition is high, the initiator (D2) does not reduce the curability of the coating film. Examples of the initiator (D2) include compounds represented by the following general formulas (D21) to (D25).

[0126] (Oxime ester-based photopolymerization initiator (D21) represented by general formula (D21)) General formula (D21) [Chemical formula]

[0127] In general formula (D21), R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. R 3 represents -COR 5 , a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. R 5 represents a phenyl group which may have a substituent. R 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl groups, cyclic alkyl groups, acyl groups, and phenyl groups of the above R 1 to R 4 may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. Note that the hydrogen atom of the substituent in R 1 to R 4 may be further substituted with another substituent R 6 . R 6represents a halogen atom, a fluorine atom, an alkyl group, a cyclic alkyl group, an acyl group, a nitro group, a sulfo group, and a phenyl group.

[0128] The oxime ester-based photoinitiator (D21) represented by the general formula (D21) is, for example, 1-[9-ethyl-6-benzoyl-9H-carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H.-Carbazol-3-yl]-ethan-1-one oxime -O-benzoate, ethanone, 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanil)benzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydro. -tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanil)methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) and the compounds represented by the following chemical formulas (D21-1) to (D21-9) can be mentioned.

[0129] [Chem.] JPEG2025098098000054.jpg47124 JPEG2025098098000055.jpg48117 JPEG2025098098000056.jpg5357

[0130] (Oxime ester-based photoinitiator (D22) represented by general formula (D22)) General formula (D22) [Chem.]

[0131] In general formula (D22), R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkyl group which may have a cyclic substituent having 3 to 20 carbon atoms, or a phenyl group. R 3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. The above-mentioned alkyl groups, cyclic alkyl groups, acyl groups, and phenyl groups of R 1 to R 3 may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atoms of the aryl group and arylalkyl group represented by R 4 may be further substituted with R 21 , -OR 21 , -COR 21 , a hydroxyl group, a nitro group, a cyano group, a halogen atom, or COOR 21 , and R 21represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R 21 The hydrogen atoms of the alkyl group, aryl group, and arylalkyl group represented by may be further substituted with a hydroxyl group, nitro group, cyano group, halogen atom, hydroxyl group, or carboxyl group. The above alkyl group, acyl group, and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. Note that R 1 ~R 4 The hydrogen atoms of the substituents in may be further substituted with other substituents.

[0132] In the general formula (D22), the linear or branched alkyl group having 1 to 20 carbon atoms represented by R 1 ~R 4 includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and the like.

[0133] In the general formula (D22), examples of the cyclic alkyl group having 3 to 20 carbon atoms represented by R 1 ~R 4 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclododecyl group, and the like.

[0134] In the general formula (D22), examples of the aryl group having 6 to 30 carbon atoms represented by R 4 , R 21 include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.

[0135] In the general formula (D22), R 4 The arylalkyl group having 7 to 30 carbon atoms represented by, for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and the like can be mentioned.

[0136] The oxime ester-based photopolymerization initiator (D22) represented by the general formula (D22) includes, for example, compounds represented by the following chemical formulas (D22-1) to (D22-10).

[0137]

Chemical formula

[0138] (The oxime ester-based photopolymerization initiator (D23) represented by the general formula (D23)) General formula (D23)

Chemical formula

[0139] In the general formula (D23), R 1 and R 2each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. R 3 , R 5 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. The above R 1 ~R 3 alkyl groups, acyl groups, and phenyl groups may be substituted with substituents selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. R 4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, or -COR 6 . R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. Note that the hydrogen atoms of the substituents in R 1 ~R 6 may be further substituted with other substituents.

[0140] In the above general formula (D23), the linear or branched alkyl group having 1 to 20 carbon atoms represented by R 1 ~R 5 includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc.

[0141] In the above general formula (D23), the R 1 ~R 5Examples of the cyclic alkyl group having 3 to 20 carbon atoms represented by

[0142] In the general formula (D23), R 4 and R 7 Examples of the heterocyclic group having 4 to 20 carbon atoms represented by include 5- to 7-membered heterocycles such as benzofuran, isobenzofuran, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazinyl, morpholinyl and the like.

[0143] In the general formula (D23), R 6 Examples of the aryl group having 6 to 30 carbon atoms represented by include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl and the like.

[0144] In the general formula (D23), R 6 Examples of the arylalkyl group having 7 to 30 carbon atoms represented by include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and the like.

[0145] Examples of the oxime ester-based photopolymerization initiator (D23) represented by the general formula (D23) include compounds represented by the following chemical formulas (D23-1) to (D23-3).

[0146]

Chemical formula

[0147] (Oxime ester-based photopolymerization initiator (D24) represented by the general formula (D24)) General formula (D24)

Chemical formula

[0148] In general formula (D24), R 1 and R 2 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. R 3 , R 5 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkoxy group which may be interrupted by a hydroxyl group. The above alkyl group, acyl group, and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. Note that the hydrogen atom of the substituent in R 1 ~R 5 may be further substituted with another substituent.

[0149] Among the above general formula (D24), the linear or branched alkyl group having 1 to 20 carbon atoms represented by R 1 ~R 5 is, for example, methyl, ethyl, propyl, isopropyl, butyl, isob tyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc.

[0150] Among the above general formula (D24), R 1 , R 2 , R 3 and R 5Examples of the cyclic alkyl group having 3 to 20 carbon atoms represented by [the formula] include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclododecyl group, and the like.

[0151] Examples of the oxime ester-based photopolymerization initiator (D2-4) represented by the general formula (D24) include 1,2-heptanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime); 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime); 1,2-octanedione, 1-[4-(benzoyl)phenyl]-, 2-(O-benzoyloxime); ethanone, 1-[4-(phenylthio)phenyl]-, octane-1-one-2-one oxime-O-acetate; 1-[4-(2-methylphenylthio)phenyl]-, octane-1-one-2-one oxime-O-acetate; 1-[4-(2,4,6-trimethylphenylthio)phenyl]-, octane-1-one-2-one oxime-O-acetate; 1-[4-(2-ethylphenylthio)phenyl]-, octane-1-one-2-one oxime-O-acetate; 1-[4-(phenylthio)phenyl]-, octane-1-one-2-one oxime-O-benzoate; 1-[4-(2-methylphenylthio)phenyl]-, octane-1-one-2-one oxime-O-benzoate; 1-[4-(2,4,6-trimethylphenylthio)phenyl]-, octane-1-one-2-one oxime-O-benzoate; 1-[4-(2-ethylphenylthio)phenyl]-, octane-1-one-2-one oxime-O-benzoate; and compounds represented by the following Chemical Formulas (D24-1) to (D24-6).

[0152] [Chemical Formula] JPEG2025098098000072.jpg7594 JPEG2025098098000073.jpg7591

[0153] (Oxime ester-based photoinitiator (D25) represented by general formula (D25)) General formula (D25) [Chemical formula]

[0154] In general formula (D25), R1 and R2 are each independently R 11 or COR 11 and represent R 11 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. The alkyl moiety of the alkyl group, aryl group, arylalkyl group, or heterocyclic group represented by R 11 may have a branched side chain or may be a cyclic alkyl and R3 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. The alkyl moiety of the alkyl group, aryl group, arylalkyl group, or heterocyclic group represented by R3 may have a branched side chain or may be a cyclic alkyl. The hydrogen atom of the aryl group, arylalkyl group, or heterocyclic group represented by R3 may be further substituted with R 21 , -OR 21 , -COR 21 , -SR 21 , -NR 22 R 23 , -CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , -NR 22 COR 21 , -OCOR 21 , -SCOR 21 , -OCSR 21 , -COSR 21 , -CSOR 21 , a hydroxyl group, a nitro group, a cyano group, a halogen atom, or COOR 21 and may be substituted R 21 、R 22 and R 23 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and R 21 、R 22 and R 23 the hydrogen atom of the alkyl group, aryl group, arylalkyl group, or heterocyclic group represented by may be further substituted with a hydroxyl group, nitro group, cyano group, halogen atom, hydroxyl group, or carboxyl group, and R 21 、R 22 and R 23 the alkylene moiety of the alkyl group, aryl group, arylalkyl group, or heterocyclic group represented by may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -,-SCO-,-COS-,-OCS- or CSO- under the condition that oxygen atoms are not adjacent to each other, R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and the alkyl moiety of the alkyl group, aryl group, arylalkyl group, or heterocyclic group represented by R 24 may have a branched side chain or may be a cyclic alkyl, R4 represents a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, or a halogen atom, and n represents 0 or 1.

[0155] In the above general formula (D25), R3, R 11 、R 21 、R 22 、R 23 and R 24The alkyl group having 1 to 20 carbon atoms represented by [alkyl group] includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and the like.

[0156] In the general formula (D25), R3, R 11 , R 21 , R 22 , R 23 and R 24 The aryl group having 6 to 30 carbon atoms represented by [aryl group] includes, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.

[0157] In the general formula (D25), R3, R 11 , R 21 , R 22 , R 23 and R 24 The arylalkyl group having 7 to 30 carbon atoms represented by [arylalkyl group] includes, for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and the like.

[0158] In the general formula (D25), R3, R 11 , R 21 , R 22 , R 23 and R 24 The heterocyclic group having 2 to 20 carbon atoms represented by [heterocyclic group] includes, for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolo Examples of the 5- to 7-membered heterocycles include pyridyl, oxazolidyl, isoxazolidyl, piperidyl, piperazinyl, morpholinyl, etc.

[0159] The method for producing the oxime ester-based photopolymerization initiator (D2) represented by the general formula (D25) is not particularly limited, and known methods can be used. For example, the method described in International Publication No. 2015 / 152153 can be used.

[0160] Examples of the oxime ester-based photopolymerization initiator (D25) represented by the general formula (D25) include compounds represented by the following chemical formulas (D25-1) to (D25-8).

[0161] Chemical formula (D25-1) Chemical formula (D25-2) Chemical formula (D25-3)

Chemical formula

[0162] Among these oxime ester-based photopolymerization initiators, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolan-2-yl)methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetoxime) are preferred.

[0163] ​Among commercially available products, there are 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) (IRGACURE OXE-01) manufactured by BASF, IRGACURE OXE-03, IRGACURE OXE-04, N-1919, NCI-730, NCI-831, NCI-930 manufactured by ADEKA, and TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-3057, TRONLY TR-PBG-309, TRONLY TR-PBG-345, TRONLY TR-PBG-3054, etc. manufactured by Changzhou Qiangli New Materials Co., Ltd. Among these, from the viewpoints of pattern formation and substrate adhesion, TRONLY TR-PBG-345, NCI-730, and NCI-930 are more preferable, and IRGACURE OXE-04 and NCI-831 are even more preferable.

[0164] The content of the oxime ester-based initiator (D2) is preferably 0.5 to 4% by mass, more preferably 1 to 2% by mass, in the non-volatile content of the photosensitive composition.

[0165] [Other polymerization initiators (D3)] The polymerization initiator (D) can contain other polymerization initiators (D3) other than the above. The other polymerization initiators (D3) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 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; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t- Benzophenone compounds such as benzoyl peroxide benzophenone; Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 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 and other tri Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime); Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine ox Side and other phosphine compounds; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; Borate compounds; Carbazole compounds; Imidazole compounds; Or titanocene compounds and the like.

[0166] Other commercially available products of polymerization initiator (D3) are, as acetophenone compounds, all IGM Resins' "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone); as for phosphine compounds, all are manufactured by IGM Resins, such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), etc.

[0167] The polymerization initiator (D) can be used alone or in combination of two or more.

[0168] From the viewpoints of adhesion, line width, and chemical resistance at low-temperature curing, the content of the polymerization initiator (D) is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and still more preferably 1 to 5% by mass in the non-volatile content of the photosensitive composition.

[0169] From the viewpoint of chemical resistance, the content of the triazine peroxide (D1) is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, and still more preferably 1 to 3% by mass in the non-volatile content of the photosensitive composition.

[0170] The mass ratio of the triazine peroxide (D1) to the oxime ester-based initiator (D2) is preferably 90:10 to 10:90, more preferably 20:80 to 80:20, and still more preferably 50:50 to 75:25.

[0171] The triazine peroxide (D1) is preferably the triazine peroxide (D1b) in terms of storage stability and the difficulty of the pattern line width becoming thick.

[0172] [Thermosetting compound (E)] The photosensitive composition of the present invention can contain a thermosetting compound (E). As a result, the thermosetting compound (E) reacts in the heating step, increasing the crosslink density and thus improving the heat resistance of the film.

[0173] Examples of the thermosetting compound (E) 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, oxetane compounds, and blocked isocyanate compounds are preferred.

[0174] (Epoxy compound (E1)) Examples of the epoxy compound (E1) include 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, naphthaldehyde, 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.), bisphenol ene, terpene, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), bisphenol Polycondensates of phenols 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 can be mentioned.

[0175] 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 manufactured by Nissan Chemical Industries, Ltd., and the like.

[0176] The epoxy compound (E1) is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0177] The epoxy equivalent of the epoxy compound (E1) is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of an epoxy compound containing 1 equivalent of epoxy groups.

[0178] From the viewpoint of chemical resistance after low-temperature heating, the epoxy compound (E1) more preferably contains a compound represented by the following general formula (110).

[0179] General formula (110)

Chemical formula

[0180] In the general formula (110), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m represents an integer from 1 to 6, and n represents an integer from 1 to 30.

[0181] R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol. The group obtained by removing m hydroxyl groups from an m-valent alcohol is preferably an alkyl group having 2 to 20 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, a methyl group, an ethyl group, a propyl group, an iso propyl group, a 2,2-dimethylpropyl group, a butyl group, an isobutyl group, a tert-butyl group, a 3,3-dimethylbutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable. m represents an integer from 1 to 6, and n represents an integer from 1 to 30. When m is 2 or more, n in the groups within each pair of parentheses in the general formula (110) may be the same or different.

[0182] Examples of the compound represented by the general formula (110) include an adduct of 1,2-epoxy-4-(2-oxiranyl)cyclohexane with 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0183] From the viewpoint of chemical resistance in low-temperature curing, the content of the epoxy compound (E1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 5 to 15% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[0184] (Oxetane compound (E2)) The oxetane compound (E2) is a compound having an oxetane group. The oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0185] 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.

[0186] Examples of commercially available products include OXE-10, 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101, 212 manufactured by Toagosei Co., Ltd.

[0187] Examples of the difunctional oxetane compound include 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 can be mentioned.

[0188] Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0189] 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 Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0190] The content of the oxetane compound (E2) 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.

[0191] (Block isocyanate compound (E3)) The block isocyanate compound (E3) is a compound having a blocked isocyanate group in which the isocyanate group is protected with the following blocking agent. Also, the block isocyanate compound (E3) does not contain an alkali-soluble group.

[0192] The blocking agents include the compounds described above. Among these, at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds is preferred, and at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferred. From the viewpoint of chemical resistance in low-temperature curing, active methylene compounds are particularly preferred. The elimination temperature of the active methylene compound or the temperature of the transesterification reaction is as low as 80 to 110 °C, and the reaction can proceed sufficiently even with low-temperature heating, improving the resistance.

[0193] Compounds having an isocyanate group include, for example, compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate; Compounds having an alicyclic structure such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane; 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Compounds having an aromatic structure such as 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis(chloromethyl)diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene, etc. are exemplified. In addition, there are exemplified burette bodies, isocyanurate bodies, adduct bodies, allophanate bodies of these compounds, and reaction products of these compounds with polyols, etc.

[0194] From the viewpoint of chemical resistance in low-temperature curing, compounds having an aliphatic structure, burette bodies, isocyanurate bodies, adduct bodies, and allophanate bodies of compounds having an alicyclic structure are preferable as the compounds having an isocyanate group. Among them, the burette body of hexamethylene diisocyanate blocked with an active methylene compound is more preferable, and the isocyanurate body of hexamethylene diisocyanate blocked with an active methylene compound is particularly preferable.

[0195] The content of the blocked isocyanate compound (E3) is preferably 0.05 to 50% by mass, more preferably 0.1 to 40% by mass, and particularly preferably 5 to 15% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[0196] The thermosetting compound (E) can be used alone or in combination of two or more. In particular, the combination of the epoxy compound (E1) and the blocked isocyanate compound (E3) is preferable from the viewpoint of chemical resistance in low-temperature curing.

[0197] [Ultraviolet absorber (F)] The photosensitive composition of the present invention can contain an ultraviolet absorber (F).

[0198] The ultraviolet absorber (F) is a compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0199] The content of the ultraviolet absorber (F) is preferably 1 to 5% by mass, more preferably 1 to 3% by mass, in the nonvolatile content of the photosensitive composition. Also, in the total of 100% by mass of the polymerization initiator (D) and the ultraviolet absorber (F), 5 to 70% by mass is preferable.

[0200] [Leveling agent (L)] The photosensitive composition of the present invention can contain a leveling agent (L). Thereby, the wettability and the drying property with respect to the substrate during coating are further improved. Examples of the leveling agent (L) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0201] Examples of the silicone surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.

[0202] 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 GmbH, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd., 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, etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0203] Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.

[0204] Examples of commercially available products include Surflon 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., and 602A of Phthalgent manufactured by Neos Co., Ltd.

[0205] The leveling agent (L) can be used alone or in combination of two or more.

[0206] The content of the leveling agent (L) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. Within this range, the balance between the coatability and the adhesiveness of the photosensitive composition is further improved.

[0207] [Dye Derivative (N)] The photosensitive composition of the present invention can contain a dye derivative (N).

[0208] The dye derivative (N) is a dispersion aid. Examples thereof include compounds having a structure in which a part of the dye is substituted with an acidic group, a basic group, a neutral group, etc. Examples of the dye derivative (N) include compounds having an acidic substituent such as a sulfo group, a carboxy group, and 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 phthalimidoalkyl group. The pigments include, for example, diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, naphthalocyanine compounds, and the like.

[0209] The pigment derivative (N) can be used alone or in combination of two or more.

[0210] [Organic solvent (O)] The photosensitive composition of the present invention can contain an organic solvent (O).

[0211] Examples of the organic solvent (O) include 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-ch Rolotoene, 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, etc. can be mentioned.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.

[0212] The organic solvent (O) can be used alone or in combination of two or more.

[0213] [Acidic resin type dispersant (S)] The photosensitive composition of the present invention contains an acidic resin type dispersant (S). As the acidic resin type dispersant (S), known resin type dispersants can be used. The acidic resin type dispersant (S) has a coloring agent affinity site that adsorbs to the dye (A) and a relaxation site that has a high affinity for components other than the dye (A) and causes steric repulsion between dispersed particles.

[0214] Examples of the acidic resin type dispersant (S) include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polysiloxanes, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides 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)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphate ester systems, and the like. Note that the acidic resin type dispersant (S) does not contain the above-mentioned block isocyanate group-containing monomer.

[0215] Examples of the acidic group include a carboxyl group, a phosphate group, a sulfonic acid group, and the like. These Among them, it is preferable to use a resin type dispersant having a carboxyl group. Examples of the resin type dispersant having a carboxyl group include a comb-shaped resin type dispersant and a linear resin type dispersant.

[0216] [Comb-shaped resin type dispersant having a carboxyl group] The comb-shaped resin type dispersant having a carboxyl group is, for example, a resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group and a tetracarboxylic dianhydride. It is a resin type dispersant which is a polymer obtained by polymerizing a monomer in the presence of a reaction product of an acid anhydride group, or a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, and a heat crosslinking group such as a hydroxyl group, a t-butyl group or an oxetane skeleton, a blocked isocyanate. It is a resin type dispersant obtained by reacting an ethylenically unsaturated monomer having an isocyanate group with a hydroxyl group of the side chain of a resin type dispersant having a side chain obtained by polymerizing a monomer having a heat crosslinking group and others. The comb-shaped resin type dispersant having a carboxyl group can also be said to be a resin having an aromatic polyester in the main chain and a graft chain which is a polymer in the monomer in the side chain.

[0217] [Linear resin type dispersant having a carboxyl group] The linear resin type dispersant having a carboxyl group can be produced, for example, by adding a tricarboxylic anhydride to a hydroxyl group using a vinyl polymer having one hydroxyl group at one end as a raw material. The linear resin type dispersant having a carboxyl group can also be said to be a vinyl polymer having an aromatic carboxyl group at the end.

[0218] The acidic resin type dispersant (S) can be used alone or in combination of two or more.

[0219] The photosensitive composition of the present invention can further contain a polymer dispersant having a basic functional group. Examples of the polymer dispersant having a basic functional group include a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer having a functional group such as a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring in the side chain, and a urethane-based polymer dispersant.

[0220] The amount of the acidic resin type dispersant (S) used is preferably about 3 to 200% by mass, more preferably about 5 to 100% by mass, based on the pigment (A). When an appropriate amount is used, the film-forming property is improved.

[0221] [Method for producing a photosensitive composition] The photosensitive composition of the present invention can be produced, for example, by adding a pigment (A), an acidic resin type dispersant (S), an alkali-soluble resin (B), an organic solvent (O), etc. and performing a dispersion treatment to produce a dispersion. Then, a polymerizable compound (C) and a polymerization initiator (D) are added to and mixed with the dispersion. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0222] 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.

[0223] The average dispersed particle diameter (secondary particle diameter) of the pigment (A) is preferably 30 to 200 nm, more preferably 40 to 200 nm. When the pigment has an appropriate particle diameter, a photosensitive composition with high dispersion stability can be easily obtained.

[0224] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using Microtrac UPA-EX150 manufactured by 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. The dilution solvent for measurement uses the organic solvent used for dispersion respectively, and when measuring the sample treated with ultrasonic waves immediately after sample preparation, results with less variation are easily obtained and are preferable. The dilution solvent for measurement uses the organic solvent used for dispersion respectively, and when measuring the sample treated with ultrasonic waves immediately after sample preparation, results with less variation are easily obtained and are preferable.

[0225] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 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 contains substantially no particles of 0.5 μm or more, and more preferably contains no particles of 0.3 μm or less.

[0226] <Color filter> The color filter of the present invention includes a substrate and a film formed from the photosensitive composition of the present invention. By appropriately selecting the type of the dye (A) to be used, the film can be used as various optical filters. For example, a red filter segment, a green filter segment, and a blue filter segment for color filter applications can be formed using an organic pigment. Alternatively, a magenta filter segment, a cyan filter segment, and a yellow filter segment can be formed. Further, a near-infrared transmission filter or a near-infrared cut filter can be formed using a near-infrared absorbing dye.

[0227] Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface. The thickness of the substrate is preferably 0.3 to 4 μm.

[0228] [Method for manufacturing a color filter] The method for manufacturing a color filter is preferably a photolithography method as far as not limited. For example, it can be manufactured by performing a step (1) of applying a photosensitive composition on a substrate to form a film, a step (2) of exposing the film in a pattern through a mask, a step (3) of alkali-developing an unexposed portion to form a patterned cured film, and a step (4) of heat-treating (post-baking) the pattern.

[0229] Hereinafter, the method for manufacturing a color filter will be described in detail. (Step (1)) The step (1) of forming a film involves applying a photosensitive composition onto a substrate by methods such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, etc. and, if necessary, drying (pre-baking) at a temperature of about 50 to 120 °C for about 10 to 120 seconds using an oven, hot plate, etc. Examples of the substrate include 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, if necessary, for improving adhesion to an upper layer, preventing diffusion of substances, and planarizing the substrate surface. The film thickness of the film is preferably 0.05 to 10.0 μm in dry film thickness, more preferably 0.3 to 5 μm.

[0230] (Step (2)) In the exposure step, the film obtained in step (1) is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, a cured film is obtained. Examples of the radiation used for exposure include ultraviolet rays such as KrF rays, g rays, h rays, and i rays.

[0231] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the unexposed portion of the film is eluted into an alkaline aqueous solution, and only the cured portion remains 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. Using at an appropriate pH suppresses pattern roughness and peeling, and improves the residual film ratio after development.

[0232] 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.

[0233] (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 80 to 180°C, more preferably 80 to 120°C, and even more preferably 80 to 100°C. Also, the heating time is preferably about 2 minutes to 1 hour, and more preferably about 3 minutes to 30 minutes.

[0234] <Image display device> The image display device of the present invention includes a color filter.

[0235] Examples of the image display device include a liquid crystal display device, an organic EL display device, etc. Hereinafter, a liquid crystal display device will be described as an example. The image display device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a gap therebetween, and liquid crystal LC is encapsulated between them.

[0236] On the inner surface of the first transparent substrate 11, a TFT (thin film transistor) array 12 is formed, and on it, a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Also, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0237] On the other hand, on the inner surface of the second transparent substrate 21, the color filter 22 of the present invention is formed. The red, green, and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0238] A transparent protective film (not shown) is formed to cover the color filter 22, and further, a transparent electrode layer 23 made of, for example, ITO is formed thereon, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0239] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

[0240] <Solid-state imaging device> The solid-state imaging device of the present invention includes a color filter. The form of 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 (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like, and has a light-shielding film with only the light-receiving portion of the photodiode opened on the photodiodes and the transfer electrodes, and a device protection film made of silicon nitride or the like formed to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. It has a configuration having a color filter on the device protection film. Further, a configuration having a condensing means (for example, a microlens or the like. The same applies hereinafter) on the device protection film and below the color filter (on the side closer to the substrate) or a configuration having a condensing means on the color filter may be used. Also, the color 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.

[0241] The imaging device including the solid-state imaging device of the present invention includes 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, etc.

Example

[0242] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto. Note that "parts" means "parts by mass" and "%" means "% by mass".

[0243] Before the examples, each measurement method will be described. The weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows.

[0244] (Average molecular weight of alkali-soluble resin and dispersed resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the alkali-soluble resin and the dispersed resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. As the apparatus, HLC-8220GPC (manufactured by Tosoh Corporation) was used. Two separation columns were connected in series, and for both packing materials, "TSK-GEL SUPERHZM-N" was connected in pairs 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 mass% of the above eluent and 20 microliters were injected. The molecular weight is in terms of polystyrene conversion.

[0245] (Acid value of alkali-soluble resin and dispersed resin) To 0.5 to 1 g of the alkali-soluble resin and dispersed 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.) to measure the acid value (mgKOH / g). 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.

[0246] (Amine value of dispersed resin) The amine value of the dispersed resin is the value obtained by converting the total measured amine value (mgKOH / g) to non-volatile content in accordance with the method of ASTM D2074.

[0247] (Production of pigment (A)) (Production of micronized pigment A-1) Anthraquinone-based red pigment C.I. Pigment Red 177 ("Sinilex Red SR3C" manufactured by Sinic Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating to 70°C to make it into a slurry state, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for a whole day and night to obtain the micronized pigment (A-1).

[0248] (Manufacture of micronized pigment A-2) Diketopyrrolopyrrole-based red pigment C.I. Pigment Red 254 ("Irgajin Red L3630" manufactured by BASF Japan Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating to 70°C to make it into a slurry state, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for a whole day and night to obtain the micronized pigment (A-2).

[0249] (Manufacture of micronized pigment A-3) Diketopyrrolopyrrole-based red pigment C.I. Pigment Red 264 ("Sinilex Red SR6T" manufactured by Sinic Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating to 70°C to make it into a slurry state, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for a whole day and night to obtain the micronized pigment (A-3).

[0250] (Manufacture of micronized pigment A-4) 100 parts of quinophthalone yellow pigment C.I. Pigment Yellow 138 (BASF Japan's "Paliotol Yellow K0960-HD"), 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. This mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating to 80 °C to make it into a slurry, and after repeating filtration and washing with water to remove salt and solvent, it was dried at 80 °C for a whole day and night to obtain a micronized pigment (A-4).

[0251] (Manufacture of micronized pigment A-5) 100 parts of isoindoline yellow pigment C.I. Pigment Yellow 139 (BASF Japan's "Paliotol Yellow D1819"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader, and kneaded at 60 °C for 10 hours. Next, this mixture was poured into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to make it into a slurry, and after repeating filtration and washing with water to remove sodium chloride and solvent, it was dried at 80 °C for a whole day and night to obtain a micronized pigment (A-5).

[0252] (Manufacture of micronized pigment A-6) 120 parts of C.I. Pigment Green 36 (Toyo Color's "Leonol Green 6YK"), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70 °C for 12 hours. This mixture was poured into 5000 parts of warm water, stirred for 1 hour while heating to about 70 °C to make it into a slurry, and after repeating filtration and washing with water to remove salt and solvent, it was dried at 80 °C for a whole day and night and pulverized to obtain a micronized pigment (A-6).

[0253] (Manufacture of micronized pigment A-7) 100 parts of C.I. Pigment Green 58 (FASTOGEN Green A110 manufactured by DIC Corporation), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless-steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 70°C for 6 hours. This kneaded product was put into 3,000 parts of warm water, stirred with a high-speed mixer for 1 hour while heating to 70°C to make it into a slurry state, and after repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night and pulverized to obtain a micronized pigment (A-7).

[0254] (Production of micronized pigment A-8) 100 parts of C.I. Pigment Green 63, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless-steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture was put into warm water, stirred with a high-speed mixer for 1 hour while heating to about 80°C to make it into a slurry state, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80°C for a whole day and night and pulverized to obtain a micronized pigment (A-8).

[0255] (Production of micronized pigment A-9) 100 parts of C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless-steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 50°C for 12 hours. This mixture was put into 3,000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70°C to make it into a slurry state, and after repeating filtration and washing with water to remove salt and solvent, it was dried at 80°C for 24 hours and pulverized to obtain a micronized pigment (A-9).

[0256] (Production of micronized pigment A-10) 100 parts of C.I. Pigment Blue 15:3 (“Leonol Blue FG7351” manufactured by Toyo Color Co., Ltd.), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. This mixture was poured into 3,000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for 24 hours and pulverized to obtain a micronized pigment (A-10).

[0257] (Production of micronized pigment A-11) 100 parts of C.I. Pigment Violet 23 (“Leonogen Violet FG6140” manufactured by Toyo Color Co., Ltd.), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. This mixture was poured into 3,000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for 24 hours and pulverized to obtain a micronized pigment (A-11).

[0258] (Production of near-infrared absorbing dye (a)) The following near-infrared absorbing dye (a) was prepared according to the examples in JP-A-2011-132361.

[0259] (Near-infrared absorbing pigment (a))

Chemical formula

[0260] 100 parts of infrared absorbing pigment (a), 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. It was kneaded together. This kneaded material was put into 3000 parts of warm water, and while heating to 70 °C, it was stirred with a high-speed mixer for 1 hour to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night and then pulverized to obtain the micronized pigment (A-12).

[0261] (Production of micronized pigment A-13) 500 parts of diketopyrrolopyrrole-based red pigment C.I. Pigment Red 269 (“Toner Magenta F8B” manufactured by Clariant), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless-steel kneader (manufactured by Inoue Seisakusho) and kneaded at 120 °C for 8 hours. Next, this kneaded material was put into 5 liters of warm water, and while heating to 70 °C, it was stirred for 1 hour to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night to obtain the micronized pigment (A-13).

[0262] (Production of micronized pigment A-14) 500 parts of perylene-based red pigment C.I. Pigment Red 179 (“Hostaphan Red P2GL” manufactured by Hoechst), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless-steel kneader (manufactured by Inoue Seisakusho) and kneaded at 120 °C for 8 hours. Next, this kneaded material was put into 5 liters of warm water, and while heating to 70 °C, it was stirred for 1 hour to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night to obtain the micronized pigment (A-14).

[0263] (Production of micronized pigment A-15) 100 parts of quinacridone-based purple pigment C.I. Pigment Violet 19 (“CATULIA RED YP” manufactured by Toyo Color Co., Ltd.), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50 °C for 12 hours. This mixture was poured into 3,000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80 °C for 24 hours and pulverized to obtain a micronized pigment (A-15).

[0264] (Manufacture of micronized pigment A-16) 100 parts of an isoindoline-based yellow pigment C.I. Pigment Yellow 185 (“Parion Yellow D1155” manufactured by BASF Japan Ltd.), 1,600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 60 °C for 10 hours. Next, this mixture was poured into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80 °C for one day and night to obtain a micronized pigment (A-16).

[0265] (Manufacture of micronized pigment A-17) 100 parts of an isoindoline-based yellow pigment C.I. Pigment Yellow 150 (“E-4GN” manufactured by Lanxess Co., Ltd.), 1,600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 60 °C for 10 hours. Next, this mixture was poured into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80 °C for one day and night to obtain a micronized pigment (A-17).

[0266] (Manufacture of alkali-soluble resin (B)) (Alkali-soluble resin (B-1) solution) Into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, propi 333 parts of propylene glycol methyl ether acetate (hereinafter referred to as PGMAc) was introduced, and after replacing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 °C. Then, a solution prepared by adding 5.0 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 a monomer methacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc was added dropwise to the flask from a dropping funnel over 2 hours while performing polymerization. The reaction was further continued at 100 °C for 5 hours. Next, the atmosphere in the flask was replaced from nitrogen to air, 43.0 parts [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)] of methacrylic acid, 0.9 part of tris(dimethylaminomethyl)phenol, and 0.145 part of hydroquinone were charged into the flask, and the reaction was continued at 110 °C for 6 hours. The reaction was terminated when the nonvolatile acid value reached 1 mgKOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added, and the reaction was carried out at 120 °C for 3.5 hours to obtain a resin solution having an acid value of 80 mgKOH / g. 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. Then, PGMAc was added so that the nonvolatile content became 40% by mass to prepare a photosensitive alkali-soluble resin (B-1) solution. The weight average molecular weight (Mw) was 9,000.

[0267] (Alkali-soluble resin (B-2) solution) Into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 333 parts of PGMAc were 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 5.0 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 a monomer methacrylate with a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours while carrying out polymerization. The reaction was further 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% based on the glycidyl groups of the glycidyl methacrylate used in this reaction)] of methacrylic acid, 0.9 part of trisdimethylaminomethylphenol, and 0.145 part of hydroquinone were charged 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 succinic 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 100 mg KOH / g. After cooling to room temperature, about 2 parts of the resin solution were sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. Then, PGMAc was added so that the nonvolatile content became 40% by mass to prepare a photosensitive alkali-soluble resin (B-2) solution. The weight average molecular weight (Mw) was 8,000.

[0268] (Alkali-soluble resin (B-3) solution) 207 parts of cyclohexanone was charged into a separable four-necked flask, which was a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device. After raising the temperature to 80 °C and purging the inside of the reaction vessel with nitrogen, from the dropping tube, 20 parts of methacrylic acid, 20 parts of a 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 2,2'-azobis- Polymerization was carried out while dropping a mixture of 0.99 parts of p-chlorobenzyl nitrile over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a resin solution. Next, with respect to the obtained resin solution, nitrogen gas was stopped, and while stirring with the injection of dry air for 1 hour, after cooling to room temperature, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 °C over 3 hours. After the dropping was completed, 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 dried by heating at 180 °C for 20 minutes to measure the non-volatile content The non-volatile content was measured. Next, cyclohexanone was added so that the non-volatile content became 40% to prepare an alkali-soluble resin (B-3) solution. The weight average molecular weight (Mw) was 22,050.

[0269] (Alkali-soluble resin (B-4) solution) 182 parts of PGMAc was 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, and a solution obtained by adding 3.0 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 a monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 136 parts of PGMAc was dropped from the dropping funnel into the flask over 2 hours while carrying out polymerization. The reaction was further continued at 100 °C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 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 charged into the flask, and the reaction was continued at 110 °C for 6 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 non-volatile content. Next, PGMAc was added so that the non-volatile content became 40% by mass to prepare an alkali-soluble resin (B-4) solution. The weight average molecular weight (Mw) was 14,960.

[0270] (Alkali-soluble resin (B-5) solution) 196 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, from the dropping tube, 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 2.0 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours while polymerizing. After completion of the dropwise addition, the reaction was continued for another 2 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 40 minutes to measure the nonvolatile content. Next, PGMAc was added so that the nonvolatile content became 40%, and an alkali-soluble resin (B-5) solution was prepared. The weight average molecular weight (Mw) was 20,000.

[0271] (Alkali-soluble resin (B-6) solution) 257.3 parts of PGMAc was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and then stirred while purging with nitrogen and the temperature was raised to 78 °C. Next, 22.4 parts of dicyclopentanyl methacrylate, 17.2 parts of methacrylic acid, 49.8 parts of methyl methacrylate, and 63.0 parts of Karenz MOI-DEM (2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester manufactured by Showa Denko K.K.) and a solution prepared by adding and dissolving 11.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) in 78.7 parts of PGMAc were added dropwise from the dropping funnel into the flask while polymerizing. After completion of the dropwise addition, the reaction was carried out at 78 °C for 3 hours. Then, PGMAc was added so that the nonvolatile content became 40 mass%, and an alkali-soluble resin (B-6) solution was prepared. The alkali-soluble resin (B-6) had an acid value of 111 mgKOH / g and a weight average molecular weight of 9,500. ​

[0272] <Synthesis of Triazine Peroxide> [Synthesis Example 1: Synthesis of Triazine Peroxide Compound 1a (D1a-1 / Compound 1)] To a 20 mL eggplant flask, 1.66 parts of ion-exchanged water and 0.553 part (6.64 mmol) of a 48% by mass aqueous sodium hydroxide solution were added, and 0.698 part (5.31 mmol) of a 69% by mass aqueous tert-butyl hydroperoxide solution was gradually added at 30 °C or lower. Here, a mixed solution of 0.500 part (2.21 mmol) of 2, 4-dichloro-6-phenyl-1,3,5-triazine and 1 mL of tetrahydrofuran was added dropwise at 10 °C over 10 minutes and reacted at 20 °C for 3.5 hours. After completion of the reaction, 10 mL of dichloromethane was added, and then the aqueous phase was separated. The organic phase was washed with ion-exchanged water and dried over anhydrous magnesium sulfate at 0 °C. After filtration, the organic phase was concentrated under reduced pressure to obtain 0.683 part (yield 92%) of the triazine peroxide compound 1a (D1a-1 / Compound 1) of the present invention.

[0273] [Synthesis Example 2: Synthesis of Triazine Peroxide Compound 2a (D1a-2 / Compound 32)] Into a 300 mL eggplant flask, 5.01 parts (31.7 mmol) of 1-methoxynaphthalene, 100 mL of dehydrated dichloromethane, and 6.12 parts (33.2 mmol) of cyanuric chloride were placed and stirred in an ice bath. After 15 minutes, 4.43 parts (33.2 mmol) of aluminum chloride was added and the temperature was raised to room temperature. After 1 hour, the reaction solution was poured into 75 mL of ice-cooled 1 M hydrochloric acid, and the aqueous phase was separated. The organic phase was washed with 100 mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, it was concentrated under reduced pressure to obtain 9.59 parts of a yellow solid as a crude product. The crude product was purified by silica gel column chromatography (n-hexane / toluene = 4 / 1 to 1.5 / 1) to obtain 8.05 (yield 83%) of 2,4-dichloro-6-(4-methoxy-1-naphthalenyl)-1,3,5-triazine.

[0274] To a 30 mL eggplant flask, 0.815 part of ion-exchanged water and 0.272 part (3.26 mmol) of a 48 mass% aqueous sodium hydroxide solution were added, and 0.276 part (2.61 mmol) of 69 mass% tert-amyl hydroperoxide was gradually added at 30 °C or lower. To this, a mixed solution of 0.300 part (1.09 mmol) of 2,4-dichloro-6-(1-naphthalenyl)-1,3,5-triazine and 3 mL of tetrahydrofuran was added dropwise at 10 °C over 10 minutes, and the reaction was carried out at 20 °C for 2 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain the triazine peroxide compound 2a (D1a-2 / compound 32) of the present invention.

[0275] [Synthesis Example 3: Synthesis of triazine peroxide compound 3a (D1a-3 / compound 37)] To a heat-dried 500 mL three-necked flask, 1.69 parts (69.5 mmol) of magnesium, 57 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were added, and the mixture was stirred at room temperature. To this, a mixed solution of 13.34 parts (50.7 mmol) of 4-bromo-4'-methoxybiphenyl and 57 mL of dehydrated tetrahydrofuran was added dropwise, and then the mixture was refluxed with stirring. After 1 hour, the internal temperature was cooled to -60 °C or lower. A separately prepared mixed solution of 8.92 parts (48.4 mmol) of cyanuric chloride and dehydrated tetrahydrofuran was added dropwise over 15 minutes. Then, the temperature was raised to room temperature over 30 minutes, and the mixture was stirred under a water bath. After 62 hours, the reaction solution was cooled in an ice bath, 1 M hydrochloric acid was added, and the pH was adjusted to 8 with a saturated aqueous sodium hydrogen carbonate solution. Next, 160 mL of ion-exchanged water was added, and the mixture was extracted with ethyl acetate. The oil phase was washed once with saturated brine and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 14.6 parts of a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 1 / 1 to 1 / 3) to obtain 5.14 parts (yield 38%) of 2,4-dichloro-6-(1-naphthalenyl)-1,3,5-triazine.

[0276] To a 30 mL eggplant flask, 0.815 part of ion-exchanged water and 0.272 part (3.26 mmol) of a 48 mass% aqueous sodium hydroxide solution were added, and 0.276 part (2.61 mmol) of 85 mass% tert-amyl hydroperoxide was gradually added at 30 °C or lower. To this, a mixed solution of 0.300 part (1.09 mmol) of 2,4-dichloro-6-(1-naphthalenyl)-1,3,5-triazine and 3 mL of tetrahydrofuran was added dropwise at 10 °C over 10 minutes, and the reaction was carried out at 20 °C for 2 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 0.216 part (yield 52%) of triazine peroxide compound 3a (D1a-3 / compound 37).

[0277] [Synthesis Example 4: Synthesis of triazine peroxide compound 4a (D1a-4 / compound 46)] Triazine peroxide compound 4a (D1a-4 / compound 46) was obtained in the same manner as in Synthesis Example 2, except that 1-methoxynaphthalene described in Synthesis Example 2 was changed to 1-bromo-4-phenyl-1,3-butadiene.

[0278] [Synthesis Example 5: Synthesis of triazine peroxide compound 1b (D1b-1 / compound 19b)] To a 100 mL eggplant flask, 3.03 parts (16.3 mmol) of diphenyl sulfide and 30 mL of dehydrated dichloromethane were added, and the mixture was cooled to 0 °C. To this, 3.00 parts (16.3 mmol) of cyanuric chloride was added, and then 2.39 parts (17.9 mmol) of aluminum chloride was added over 10 minutes, and the reaction was carried out at 0 °C for 3 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice-cooled 1 M hydrochloric acid and stirred, and the aqueous phase was separated. The organic phase was washed with 50 mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, the solution was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 4 / 1 to 2 / 1) to obtain 5.03 parts (yield 92.6%) of 2,4-dichloro-6-(4-phenylthio-1-phenyl)-1,3,5-triazine.

[0279] To a 100 mL eggplant flask, 3.00 parts (8.98 mmol) of 2,4-dichloro-6-(4-phenylthio-1-phenyl)-1,3,5-triazine and 30 mL of methyl ethyl ketone were added, and the mixture was heated to 40 °C. After adding 4.67 parts of ion-exchanged water and 4.31 parts (26.9 mmol) of 25% by mass aqueous sodium hydroxide solution, 0.32 part (9.87 mmol) of methanol was added dropwise over 10 minutes, and the reaction was carried out at 40 °C for 2 hours. At 40 °C or lower, 1.29 parts (9.87 mmol) of 69% by mass aqueous tert-butyl hydroperoxide solution was added dropwise over 10 minutes, and the reaction was carried out at 40 °C for 1 hour. After completion of the reaction, the aqueous phase was separated, and the organic phase was poured into 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 2.60 parts (yield 75.5%) of the triazine peroxide compound 1b (D1b-1 / compound 19) of the present invention.

[0280] [Synthesis Example 6: Synthesis of triazine peroxide compound 2b (D1b-2 / compound 25b)] The triazine peroxide compound 2b (D1b-2 / compound 25b) was obtained in the same manner as in Synthesis Example 1, except that diphenyl sulfide used in Synthesis Example 1 was changed to 1-methoxynaphthalene.

[0281] [Synthesis Example 7: Synthesis of triazine peroxide compound 3b (D1b-3 / compound 35b)] To a heat-dried 100 mL three-necked flask, 0.44 part (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were added, and the mixture was stirred at room temperature. 4.29 parts (16.3 mmol) of 4-bromo-4'-methoxybiphenyl and dehydrated te After dropping a mixed solution of 15 mL of tetrahydrofuran, the mixture was refluxed and stirred for 1 hour. In another 100 mL three-necked flask, 3.00 parts (16.3 mmol) of cyanuric chloride and 15 mL of dehydrated tetrahydrofuran were added and cooled to 0 °C. The previously prepared mixed solution was dropped here over 30 minutes, raised to room temperature, and stirred for 15 hours. The reaction solution was cooled in an ice bath, 1 M hydrochloric acid was added and stirred, and the pH was adjusted to 8 with a saturated aqueous sodium hydrogen carbonate solution. Then, it was extracted with ethyl acetate. The oil phase was washed once with saturated brine and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 3 / 1 to 1 / 1) to obtain 2.07 parts (yield 38.2%) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine. was obtained.

[0282] Into a 50 mL eggplant flask, 1.20 parts (3.62 mmol) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl) -1,3,5-triazine and 10 mL of methyl ethyl ketone were added and heated to 40 °C. After adding 1.88 parts of ion-exchanged water and 1.74 parts (10.9 mmol) of 25 mass% aqueous sodium hydroxide solution, 0.13 part (3.98 mmol) of methanol was dropped over 5 minutes and reacted at 40 °C for 2 hours. An aqueous solution of 69 mass% tert-butyl hydroperoxide (0.52 part, 3.98 mmol) was dropped over 5 minutes at 40 °C or lower and reacted at 40 °C for 1 hour. After completion of the reaction, the aqueous phase was separated, and the oil phase was poured into 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 1.04 parts (yield 75.0%) of the triazine peroxide compound 3b (D1b-3 / compound 35b) of the present invention.

[0283] [Synthesis Example 8: Synthesis of Triazine Peroxide Compound 4b (D1b-4 / Compound 48b)] Triazine peroxide compound 4b (D1b-4 / Compound 48b) was obtained in the same manner as in Synthesis Example 7, except that the methanol used in Synthesis Example 7 was changed to ethanol, and the 69% by mass aqueous tert-butyl hydroperoxide solution was changed to an 85% by mass tert-amyl hydroperoxide solution.

[0284] [Synthesis Example 9: Synthesis of Triazine Peroxide Compound 5b (D1b-5 / Compound 53b)] Triazine peroxide compound 5b (D1b-5 / Compound 53b) was obtained in the same manner as in Synthesis Example 7, except that the methanol used in Synthesis Example 7 was changed to isopropyl alcohol, and the 69% by mass aqueous tert-butyl hydroperoxide solution was changed to a 90% by mass tert-hexyl hydroperoxide solution.

[0285] [Synthesis Example 10: Synthesis of Triazine Peroxide Compound 6b (D1b-6 / Compound 56b)] Triazine peroxide compound 6b (D1b-6 / Compound 56b) was obtained in the same manner as in Synthesis Example 7, except that the methanol used in Synthesis Example 7 was changed to tert-butyl alcohol, and the 69% by mass aqueous tert-butyl hydroperoxide solution was changed to an 80% by mass cumene hydroperoxide solution.

[0286] [Synthesis Example 11: Synthesis of Triazine Peroxide Compound 7b (D1b-7 / Compound 77b)] To a heat-dried 100 mL three-necked flask were added 0.44 part (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine, and the mixture was stirred at room temperature. 4.29 parts (16.3 mmol) of 4-bromo-4'-methoxybiphenyl and dehydrated te After dropping a mixed solution of 15 mL of tetrahydrofuran, the mixture was refluxed and stirred for 1 hour. In another 100 mL three-necked flask, 3.00 parts (16.3 mmol) of cyanuric chloride and 15 mL of dehydrated tetrahydrofuran were added and cooled to 0 °C. The previously prepared mixed solution was dropped into this flask over 30 minutes, the solution temperature was raised to 25 °C, and the mixture was stirred for 15 hours to carry out the reaction. After the reaction was completed, the solution was cooled in an ice bath, 1 M hydrochloric acid was added and stirred, and the pH was adjusted to 8 with a saturated aqueous sodium hydrogen carbonate solution. Then, extraction was performed with ethyl acetate. The organic phase was washed once with saturated brine and then dehydrated with magnesium sulfate. After filtration, the organic phase was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 3 / 1 to 1 / 1) to obtain 2.07 parts (yield 38.2%) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine. 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine was obtained.

[0287] To a 100 mL eggplant flask, 3.03 parts (16.3 mmol) of anisole and 30 mL of dehydrated dichloromethane were added and cooled to 0 °C. To this, 3.00 parts (16.3 mmol ) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine were added, and then 2.39 parts (17.9 mmol) of aluminum chloride were added over 10 minutes, and the reaction was carried out at 0 °C for 3 hours. After the reaction was completed, the reaction solution was poured into 50 mL of ice-cooled 1 M hydrochloric acid and stirred, and the aqueous phase was separated. The organic phase was washed with 50 mL of saturated brine and dehydrated with anhydrous sodium sulfate . After filtration, concentration under reduced pressure was carried out to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 4 / 1 to 2 / 1) to obtain 5.03 parts (yield 92.6%) of 2-chloro-4-(4-methoxyphenyl)-6-[4-(4'-methoxybiphenyl )]-1,3,5-triazine.

[0288] To a 50 mL eggplant flask, 1.88 parts of ion-exchanged water and 1.74 parts (10.9 mmol) of a 25 mass% aqueous sodium hydroxide solution were added, and 0.52 part (3.98 mmol) of a 69 mass% aqueous tert-butyl hydroperoxide solution was gradually added at 30 °C or lower. To this, a mixed solution of 1.20 parts (3.62 mmol) of 2-chloro-4-(4-methoxyphenyl)-6-[4-(4'-methoxybiphenyl)]-1 ,3,5-triazine and 10 mL of tetrahydrofuran was added dropwise at 10 °C over 10 minutes, and the mixture was reacted at 20 °C for 3 hours. After completion of the reaction, 10 mL of dichloromethane was added, and the aqueous phase was separated. The organic phase was washed with ion-exchanged water and dried over anhydrous magnesium sulfate at 0 °C. After filtration, the organic phase was concentrated under reduced pressure to obtain 1.04 parts (yield 75.0%) of the triazine peroxide compound 7b (D1b-7 / compound 77b) of the present invention.

[0289] [Synthesis Example 12: Synthesis of triazine peroxide compound 8b (D1b-8 / compound 81b)] To a 100 mL eggplant flask, 3.00 parts (16.3 mmol) of cyanuric chloride, 30 mL of dehydrated dichloromethane, and 4.35 parts (32.6 mmol) of aluminum chloride were added, and the mixture was cooled to 20 °C. To this, 5.16 parts (32.6 mmol) of 1-methoxynaphthalene was added over 15 minutes, and the mixture was reacted at 20 °C for 3 hours. After completion of the reaction, the reaction solution was cooled to 0 °C, 50 mL of ice-cooled 1 M hydrochloric acid was added and stirred, and the aqueous phase was separated. The organic phase was washed with 50 mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, it was concentrated under reduced pressure to obtain 5.48 parts (yield 78.6%) of a crude product of 2-chloro-4,6-bis(4-methoxy-1-naphthalenyl)-1,3,5-triazine.

[0290] To a 100 mL eggplant flask, 3.00 parts (5.45 mmol) of the crude 2-chloro-4,6-bis(4-methoxy-1-naphthalenyl)-1,3,5-triazine and 30 mL of tetrahydrofuran were added, and the mixture was heated to 40 °C. To this, a mixture of 2.18 parts (10.9 mmol) of a 20% by mass aqueous sodium hydroxide solution and 1.42 parts (10.9 mmol) of a 69% by mass aqueous tert-butyl hydroperoxide solution was added dropwise over 10 minutes, and the reaction was carried out at 40 °C for 4 hours. After completion of the reaction, 50 mL of dichloromethane was added, and the aqueous phase was separated. The organic phase was washed with ion-exchanged water and dried over anhydrous magnesium sulfate at 0 °C. After filtration, the mixture was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (using dichloromethane) to obtain 1.63 parts (yield 62.3%) of the triazine peroxide compound 8b (D1b-8 / Compound 81b) of the present invention.

[0291] <Production of Acidic Resin-Type Dispersant (S)> (Acidic Resin-Type Dispersant (S-1) Solution) To a 500 mL round-bottomed four-neck separable flask equipped with a condenser, dropping funnel, nitrogen inlet tube, stirrer, and thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethyl ketene methyl trimethylsilyl acetal as an initiator were added via the dropping funnel, and sufficient nitrogen substitution was carried out. 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 were added dropwise over 60 minutes using the dropping 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 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 block copolymer THF solution was reprecipitated in hexane and purified by filtration and vacuum drying. Next, 15.0 parts by mass of the obtained block copolymer were dissolved in 35 parts by mass of propylene glycol monomethyl ether acetate (PGMAc) in a 100 mL round-bottom flask, and 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalent to dimethylaminopropyl methacrylamide), which is a salt-forming component, was added. The mixture was stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to adjust the content, obtaining an acidic resin-type dispersant (S-1) solution with a non-volatile content of 40%.

[0292] (Acidic resin type dispersant (S-2) solution) In a reaction vessel equipped with a nitrogen inlet tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-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 to 50°C with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and 0.1 parts of 2,2'-azobisisobutyronitrile was added to 90 parts of PGMAc to form a solution. The reaction was continued for 7 hours while adding the liquid. The reaction was confirmed to be 95% by measuring the non-volatile content. Next, 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued for 7 hours at 100°C. The reaction was terminated when the acid value was confirmed to be 98% or more of the acid anhydride was half-esterified, and the non-volatile content was diluted with PGMAc to 40%, obtaining a comb-shaped acidic resin-type dispersant (S-2) solution with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500.

[0293] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed for 3 hours in an Eiger mill (Eiger Japan's "Mini Model M-250MKII") using zirconia beads with a diameter of 0.5 mm, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1 with a non-volatile content of 20%. The organic solvent (O-1) was PGMAc. Micronized pigment (A-1): 12.00 parts Solution of acidic resin dispersant (S-1): 10.00 parts Solution of acidic resin dispersant (S-2): 10.00 parts Organic solvent (O-1): 68.00 parts

[0294] The dispersions 1 to 18 were obtained in the same manner as dispersion 1, except that the materials and compounding amounts of the above dispersion 1 were changed as described in Tables 1-1 and 1-2.

[0295]

Table 1-1

[0296]

Table 1-2

[0297] Details of the abbreviations in Table 1 are as follows. Dye derivative (N-1)

Chemical formula

[0298] Dye derivative (N-2)

Chemical formula

[0299] Dye derivative (N-3)

Chemical formula

[0300] Dye derivative (N-4)

Chemical formula

[0301] Dye derivative (N-5)

Chemical formula

[0302] Fine-particle pigment (A-18): Carbon black ("#850" manufactured by Mitsubishi Chemical Corporation)

[0303] <Manufacture of photosensitive composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive composition 1 with a nonvolatile content of 15%. A photosensitive composition 1 with a nonvolatile content of 15% was obtained. Dispersion 4: 11.25 parts Dispersion 5: 3.75 parts Dispersion 6: 22.50 parts Alkali-soluble resin (B-1) solution: 7.88 parts Polymerizable compound (C-2): 3.00 parts Polymerization initiator (Da-1): 0.30 part Polymerization initiator (D2-1): 0.15 part Thermosetting compound (E-1): 0.75 part Ultraviolet absorber (F-1): 0.15 part Leveling agent (L): 1.00 part Organic solvent (O): 49.28 parts

[0304] [Polymerizable compound (C)] · C-1: NK Ester A-DCP (tricyclodecane dimethanol diacrylate bifunctional acrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) · C-2: Aronix M-306 (mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate trifunctional to tetrafunctional acrylate: manufactured by Toagosei Co., Ltd.) · C-3: Aronix M-402 (dipentaerythritol penta and hexaacrylate pentafunctional to hexafunctional acrylate: manufactured by Toagosei Co., Ltd.) · C-4: UA-306H (hexafunctional urethane acrylate: manufactured by Kyoeisha Chemical Co., Ltd.) · C-5: Aronix M-520 (polybasic acid-modified acrylic oligomer pentafunctional acrylate: manufactured by Toagosei Co., Ltd.)

[0305] [Coinitiator (D)] · D1a-1: Compound 1 of the triazine peroxide (D1a) · D1a-2: Compound 32 of the triazine peroxide (D1a) · D1a-3: Compound 37 of the triazine peroxide (D1a) · D1a-4: Compound 46 of the triazine peroxide (D1a) · D1b-1: Compound 19b of the triazine peroxide (D1b) · D1b-2: Compound 25b of the triazine peroxide (D1b) · D1b-3: Compound 35b of the triazine peroxide (D1b) · D1b-4: Compound 48b of the triazine peroxide (D1b) · D1b-5: Compound 53b of the triazine peroxide (D1b) · D1b-6: Compound 56b of the triazine peroxide (D1b) · D1b-7: Compound 77b of the triazine peroxide (D1b) · D1b-8: Compound 81b of the triazine peroxide (D1b) · D2-1: Adeka Arcles NCI-831 (manufactured by ADEKA; oxime-based photoinitiator (D21) represented by chemical formula (D21-2)) · D2-2: PBG-345 (manufactured by Changzhou Qiangli; oxime-based photoinitiator (D22) represented by chemical formula (D22-1)) · D2-3: Irgacure OXE-04 (manufactured by BASF Japan; oxime-based photoinitiator (D23) represented by chemical formula (D23-1)) · D2-4: Irgacure OXE-01 (manufactured by BASF Japan; oxime-based photoinitiator (D24) represented by chemical formula (D24-1)) · D2-5: Adeka Cruze NCI-730 (manufactured by ADEKA; oxime-based photoinitiator (D25) represented by chemical formula (D25-6)) · D3-1: Irgacure 907 (α-aminoalkylphenone; manufactured by BASF Japan) ·D3-2: Irgacure 369 (α-aminoalkylphenone; manufactured by BASF Japan Ltd.) ·D3-3: NPI-20400 (α-aminoalkylphenone; manufactured by Changzhou Qiangli Co., Ltd.)

[0306] [Thermosetting compound (E)] ·E-1: EHPE-3150 (epoxy compound; manufactured by Daicel Chemical Industries, Ltd.) ·E-2: Denacol EX-611 (epoxy compound; manufactured by Nagase Sangyo Co., Ltd.) ·E-3: Duranate MF-K60B (isocyanurate form of hexamethylene diisocyanate blocked with an active methylene compound; manufactured by Asahi Kasei Corporation) ·E-4: Aron Oxetane OXT-121 (oxetane compound; manufactured by Toagosei Co., Ltd.)

[0307] [UV absorber (F)] ·F-1: Tinuvin 326 (2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole; manufactured by BASF Japan Ltd.)

[0308] [Leveling agent (L)] A mixed solution prepared by mixing 1 part each of BYK-330 (manufactured by BYK Chemie GmbH) and Megafac F-551 (manufactured by DIC Corporation) and dissolving them in 98 parts of PGMAc was used as the leveling agent (L).

[0309] [Organic solvent (O)] A mixture of 80 parts of propylene glycol monomethyl ether acetate, 10 parts of cyclohexanone, and 10 parts of ethyl 3-ethoxypropionate was used as the organic solvent (O).

[0310] ​The photosensitive compositions of Examples 2 to 70 and Comparative Example 1 were obtained in the same manner as in Example 1, except that the types and amounts of the components were changed so that the compositions of Example 1 were in the ratios described in Tables 2 to 8. Hereinafter, in the tables, the content of D1 is the content of triazine peroxide (D1) in the non-volatile matter of the photosensitive composition. The mass ratio of D1 to D2 is the mass ratio of triazine peroxide (D1): oxime ester-based initiator (D2).

[0311]

Table 2

[0312]

Table 3

[0313]

Table 4

[0314]

Table 5

[0315]

Table 6

[0316]

Table 7

[0317]

Table 8

[0318] <Evaluation of Photosensitive Composition> For the obtained Examples 1 to 70 and Comparative Example 1, the evaluation of line width, adhesion, and chemical resistance was carried out by the following methods. The evaluation results are shown in Table 9.

[0319] [Line Width Evaluation] The obtained photosensitive composition was applied onto 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 in thickness using a spin coater so that the dry film thickness became 3.0 μm, and dried on a hot plate at 90°C for 2 minutes. Next, using an ultra-high pressure mercury lamp, with an illuminance of 30 mW / cm 2 , 100 mJ / cm 2 exposure was performed through a photomask with a 50-μm-wide stripe pattern. Further, after cooling this substrate to room temperature, an organic alkaline developer, tetramethylammonium hydroxide (hereinafter referred to as TMAH), was used for spray development at 23°C for 70 seconds, washed with ion-exchanged water, air-dried, and heated in a clean oven at 100°C for 20 minutes to form a stripe pattern on the substrate. The pattern was observed with an optical microscope to evaluate the line width. The evaluation criteria are as follows, and 2 or more are within the practical range. 4: -1 μm ≤ line width ≤ 1 μm from the mask opening. 3: -3 μm ≤ line width < -1 μm or 1 μm < line width ≤ 3 μm from the mask opening. 2: -5 μm ≤ line width < -3 μm or 3 μm < line width ≤ 5 μm from the mask opening. 1: line width < -5 μm or line width > 5 μm from the mask opening.

[0320] [Adhesion Evaluation] The obtained photosensitive composition was applied onto 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 in thickness by the spin coating method so that the film thickness after drying became 3.0 μm, and dried on a hot plate at 90°C for 2 minutes. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, with an illuminance of 30 mW / cm through a photomask of stripe patterns with widths of 5, 10, 15, 20, and 25 μm in 5-μm increments 2 , 100 mJ / cm 2It was exposed. Then, this substrate was spray-developed using TMAH at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 100°C for 20 minutes to obtain a substrate for evaluation. The spray development was performed at the shortest time capable of forming a pattern without residue for each film of the photosensitive composition, and this was defined as the appropriate development time. Regarding the fine line patterns with a width of 5 to 25 μm among the patterns of the substrate for evaluation, they were observed with an optical microscope, and the minimum line width of the remaining fine line patterns was confirmed. The evaluation criteria are as follows, and 2 or more are within the practical range. 4: Fine lines of 10 μm or less remain. 3: Fine lines exceeding 10 μm and 15 μm or less remain. 2: Fine lines exceeding 15 μm and 20 μm or less remain. 1: No fine lines of 20 μm or less remain.

[0321] [Chemical resistance evaluation] The substrate prepared in the same manner as in the adhesion evaluation was measured for the chromaticity ([L*(1), a*(1), b*(1)]) of a 100-μm-wide stripe pattern with a C light source using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Then, it was immersed in N-methylpyrrolidone for 30 minutes, washed with ion-exchanged water, and air-dried. Next, the chromaticity ([L*(2), a*(2), b*(2)]) of the 100-μm-wide stripe pattern with a C light source was measured, and the color difference ΔE*a*b* was obtained using the following calculation formula. The evaluation criteria are as follows, and 2 or more are within the practical range. ΔE*a*b* = {(L*(2) - L*(1)) 2 +(b*(2) - b*(1)) 2 +(a*(2) - a*(1)) 2} 0.5 4: ΔE*a*b* is less than 1 3: ΔE*a*b* is 1 or more and less than 2. 2: ΔE*a*b* is 2 or more and less than 3. 1: ΔE*a*b* is 3 or more.

[0322]

Table 9

Explanation of Symbols

[0323] 10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizer 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizer 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims

1. A photosensitive composition for a color filter, comprising a dye (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an acidic resin-type dispersant (S), The polymerization initiator (D) contains at least one of a triazine peroxide (D1a) represented by the following general formula (1a) and a triazine peroxide (D1b) represented by the following general formula (1b): General formula (1a) 【Chemistry 1】 (In general formula (1a), R １ and R ３ R independently represents a methyl group or an ethyl group. ２ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group; X represents an aromatic ring-containing group, and n represents an integer of 0 to 2. General formula (1b) 【Chemistry 2】 (In general formula (1b), R １ and R ２ are independently a methyl group or an ethyl group, R ３ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group; R ４ represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -Y-R, or -N-RR', where Y is an oxygen atom or represents a sulfur atom, and R and R' are independently a hydrogen atom or an optionally substituted C X represents an aliphatic hydrocarbon group having 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, or a heterocyclic group having 2 to 20 carbon atoms which may be substituted. X represents an aromatic ring-containing group.

2. The photosensitive composition for color filters according to claim 1 , further comprising a thermosetting compound (E).

3. 2. The photosensitive composition for color filters according to claim 1, wherein the polymerization initiator (D) further comprises an oxime ester initiator (D2).

4. A substrate and a photosensitive composition for color filters according to any one of claims 1 to 3. A color filter comprising a coating formed of:

5. An image display device comprising the color filter according to claim 4 .

6. A solid-state imaging device comprising the color filter according to claim 4 .

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