Photosensitive composition for color filter, color filter, image display device, and solid-state imaging element

Abstract

The purpose of the present invention is to provide a photosensitive composition for a color filter, a color filter, an image display device, and a solid-state imaging element, said photosensitive composition being capable of forming a coating film having excellent line width, adhesion, and chemical resistance of a pattern that is formed even when a heating step is at a low temperature. A photosensitive composition containing a dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), the polymerization initiator (D) being a triazine peroxide (D1a) represented by general formula (1a) or a triazine peroxide (D1b) represented by general formula (1b). General formula (1a) [chemical] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a photosensitive composition for a color filter, a color filter, an image display device, and a solid-state imaging element. Background Art

[0002] The demand for optical filters used in liquid crystal display devices, digital cameras, smartphones, infrared sensors, etc. is increasing due to the popularity of these devices. In addition, organic electroluminescence (EL) display devices such as organic light emitting diodes (OLEDs) that do not require backlights are being studied, as they are lightweight, thin, and power-efficient. Organic materials for photoelectron conversion films in image sensors are also being studied.

[0003] Since the organic light-emitting layer used in an organic EL display device or the like generally has low heat resistance, the photosensitive composition for forming a color filter used in an organic EL display device is preferably subjected to a heating step at a low temperature, for example, 150° C. or lower.

[0004] Therefore, Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble resin having an alkoxysilyl group.

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2020-186325 Summary of the invention

[0008] [Problems to be solved by the invention]

[0009] However, in conventional photosensitive compositions, the line width, adhesion, and chemical resistance of patterns formed in a heating process at 120° C. or less are not at a satisfactory level.

[0010] An object of the present invention is to provide a photosensitive composition for a color filter which can form a film having excellent line width, adhesion, and chemical resistance of a formed pattern even in a heating step at a low temperature.

[0011] [Technical means to solve the problem]

[0012] The photosensitive composition for color filter of the present invention is a photosensitive composition for color filter, comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an acidic resin dispersant (S).

[0013] The polymerization initiator (D) contains one or more of a peroxytriazine (D1a) represented by the following general formula (1a) and a peroxytriazine (D1b) represented by the following general formula (1b).

[0014] General formula (1a)

[0015] [Chemistry 1]

[0016]

[0017] (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 is a group containing an aromatic ring, and n represents an integer from 0 to 2)

[0018] General formula (1b)

[0019] [Chemistry 2]

[0020]

[0021] (In 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 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, -CO-R, -YR, or -N-RR', wherein Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, 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 a group containing an aromatic ring)

[0022] The color filter of the present invention includes a substrate and a coating film formed from the photosensitive composition for color filter.

[0023] The image display device of the present invention includes the color filter.

[0024] A solid-state imaging device according to the present invention includes the above-mentioned color filter.

[0025] [Effects of the Invention]

[0026] According to the present invention, a photosensitive composition for a color filter can be provided, which can form a film having excellent line width, adhesion and chemical resistance of the formed pattern even if the heating process is low temperature. In addition, the present invention can provide a color filter, an image display device, and a solid-state imaging element. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a schematic cross-sectional view of an image display device.

[0028] [Explanation of Symbols]

[0029] 10: Liquid crystal display device (image display device)

[0030] 11: Transparent substrate

[0031] 12: TFT array

[0032] 13: Transparent electrode layer

[0033] 14: Orientation layer

[0034] 15: Polarizing plate

[0035] 21: Transparent substrate

[0036] 22: Color filter

[0037] 23: Transparent electrode layer

[0038] 24: Orientation layer

[0039] 25: Polarizing plate

[0040] 30: Backlight unit

[0041] 31: White LED light source

[0042] LC: liquid crystal DETAILED DESCRIPTION

[0043] The following are definitions of the terms used in this specification. When expressed as "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, they represent "acryloyl and / or methacryloyl", "acrylic acid and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively.

[0044] "CI" refers to Colour Index (CI).

[0045] The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group. The monomer is the state before polymerization. The monomer unit is the state constituting the resin after polymerization.

[0046] The photosensitive composition for color filter of the present invention (hereinafter also referred to as photosensitive composition) is a photosensitive composition comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an acidic resin dispersant (S), wherein the polymerization initiator (D) contains one or more of a peroxy triazine (D1a) represented by the general formula (1a) and a peroxy triazine (D1b) represented by the general formula (1b). The photosensitive composition of the present invention is used to form a film. The film is preferably used for a color filter.

[0047] The film formed by the photosensitive composition of the present invention contains a peroxy triazine (D1a) represented by the general formula (1a) or a peroxy triazine (D1b) represented by the following general formula (1b), and thus has photopolymerization properties that can efficiently absorb light of a wavelength of 365 nm or the like to generate free radicals during exposure. Furthermore, it also has thermal polymerization properties that can generate free radicals by heat, so the film will harden even if the heating process is low temperature. As a result, when a pattern is formed by photolithography, the line width of the pattern is not easy to become fat, and a high-precision pattern is easily formed. Furthermore, a film having good pattern adhesion and excellent chemical resistance can be formed.

[0048] <Pigment (A)>

[0049] Examples of the colorant (A) include pigments, dyes, and near infrared absorbing colorants. Examples of the colorant include inorganic pigments and organic pigments.

[0050] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 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, 58:3 :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, 248 9, 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.

[0051] Examples of the orange pigment include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0052] Examples of yellow pigments include CI 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, CI Pigment Yellow 138, 139, 150, 185, 231, and 233 are preferred.

[0053] Examples of green pigments include CI 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, and 63. Among these, CI Pigment Green 7, 36, 58, 59, 62, and 63 are preferred.

[0054] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 16 are preferred.

[0055] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0056] Examples of the black pigment include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0057] Further, inorganic pigments such as titanium oxide, barium sulfate, zinc flower, lead sulfate, chrome yellow, zinc yellow, red iron (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black are mentioned.

[0058] Near infrared absorbing pigments are compounds having maximum absorption in the range of wavelengths of 700 nm to 2,000 nm. Examples of near infrared absorbing pigments include pigments (also referred to as near infrared absorbing pigments) or dyes (also referred to as near infrared absorbing dyes). In addition, near infrared absorbing pigments and near infrared absorbing dyes may also be used in combination. In addition, from the viewpoint of heat resistance, near infrared absorbing pigments are preferably near infrared absorbing pigments.

[0059] 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 still more preferably 0.5 g or less.

[0060] Examples of near infrared absorbing pigments include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, iminium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and crotonium compounds. Among these, naphthalocyanine compounds, pyrrolopyrrole compounds, and squarylium compounds are preferred from the viewpoint of heat resistance, and naphthalocyanine compounds and squarylium compounds are more preferred.

[0061] (Squarylium compounds)

[0062] Specific examples of the squarylium compounds are shown below, but the present invention is not limited to these.

[0063] [Chemistry 3]

[0064]

[0065] [Chemistry 4]

[0066]

[0067] (Pyrrolopyrrole compounds)

[0068] The pyrrolopyrrole compound is preferably a compound represented by the following general formula (5).

[0069] General formula (5)

[0070] [Chemistry 5]

[0071]

[0072] (In general formula (5), R 1x and R1y Each independently represents an alkyl group, an aryl group or a heteroaryl group, R 2 and R 3 Each independently represents a hydrogen atom or a substituent, R 2 and R 3 Can bond with 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 metal atom, R 4 Can be selected with R 1x , R 1y and R 3 At least one of the groups is covalently bonded or coordinately bonded. 4X , R 4Y Each independently represents a substituent. The compound represented by the general formula (5) is described in Japanese Patent Application Publication No. 2009-263614, Japanese Patent Application Publication No. 2011-68731, and International Publication No. 2015 / 166873.

[0073] Specific examples of the pyrrolopyrrole compound are shown below. In the following structural formula, Me represents a methyl group, and Ph represents a phenyl group. In addition, the present invention is not limited to these.

[0074] [Chemistry 6]

[0075]

[0076] (Naphthalocyanine compounds)

[0077] The naphthalocyanine compound is preferably a compound represented by the following general formula (6).

[0078] General formula (6)

[0079] [Chemistry 7]

[0080]

[0081] In the 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 , 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.

[0082] R in formula (6) 1 To R 24 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0083] In the general formula (6), M represents two hydrogen atoms, a metal atom, a metal oxide or a metal halide. When M represents two hydrogen atoms, the part forming NMN in the general formula (6) is represented by two NH structures. As the metal atom represented by M in the general formula (6), iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium and tin can be listed. As the metal oxide represented by M in the general formula (6), titanium oxide and vanadium oxide can be listed. As the metal halide represented by M in the general formula (6), aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride and silicon chloride can be listed. As M in the general formula (6), copper, zinc, cobalt, nickel, iron, vanadium oxide, titanium oxide, indium chloride or tin (II) chloride are preferred, copper, zinc, vanadium oxide or titanium oxide are more preferred, and vanadium oxide is particularly preferred.

[0084] Specific examples of the compound represented by the general formula (6) are shown below, but the present invention is not limited to these.

[0085] [Chemistry 8]

[0086]

[0087] [Chemistry 9]

[0088]

[0089] [Chemistry 10]

[0090]

[0091] The naphthalocyanine compounds represented by the general formula (6) may be used alone or in combination of two or more.

[0092] The naphthalocyanine compound represented by the general formula (6) is preferably a compound having a maximum absorption wavelength in the wavelength region of 750 nm to 1500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength region of 780 nm to 1000 nm.

[0093] Furthermore, the naphthalocyanine compound is preferably a compound represented by the following general formula (7).

[0094] General formula (7)

[0095] [Chemistry 11]

[0096]

[0097] In the 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 alkoxy 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.

[0098] Z is a polymer moiety composed of a monomer unit represented by the general formula (8), or a phosphorus compound moiety represented by the general formula (9).

[0099] [Chemistry 12]

[0100]

[0101] In the general formula (8), X represents -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 linked to each other via -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. 31 represents hydrogen or methyl. n is 0 or an integer of 1 to 10. * represents a bond with Al.

[0102] In the general formula (9), R 29 and R 30 each independently represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, and R 29 With R 30 They can bond to each other to form a ring. * is a bond with Al.

[0103] Specific examples of the compound represented by the general formula (7) are shown below, but the present invention is not limited to these.

[0104] [Chemistry 13]

[0105]

[0106] [Chemistry 14]

[0107]

[0108] Near infrared absorbing pigment can be used alone or in combination of two or more. In the case of using two or more, it is preferred to use compounds with different maximum absorption wavelengths. Thus, compared with the case of using a near infrared absorbing pigment, the waveform of the absorption spectrum is broadened, and near infrared rays of a wide wavelength range can be absorbed.

[0109] (dye)

[0110] Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. In addition, the dye may be a derivative thereof or a lake pigment obtained by lake-forming the dye.

[0111] Acid dyes preferably have acidic groups such as sulfonic acid groups or carboxylic acid groups. Direct dyes are preferably salt-forming compounds of inorganic salts of acid dyes, or acid dyes and nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds. In addition, salts of resin components with these functional groups and acid dyes, i.e., salt-forming compounds, are also preferably used. In addition, the salt-forming compound is modified into a sulfonic acid amide compound by sulfonamidation, thereby easily obtaining a photosensitive composition with excellent tolerance (light resistance, solvent resistance).

[0112] In addition, a salt compound of an acid dye and a compound having an onium salt group is also preferred because of its excellent resistance (light resistance, solvent resistance). In addition, the compound having an onium salt group is preferably a resin having a cationic group.

[0113] Basic dyes can be used directly, but are preferably salt compounds that are salified with organic acids or perchloric acid or their metal salts. The salt compounds of basic dyes are preferably preferred because of excellent tolerance (light resistance, solvent resistance) or affinity with pigment. In addition, in the salt compounds of basic dyes, the anionic component that plays a role as a counter ion is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorinated phosphorus anionic compound, a fluorinated boron anionic compound, a cyano-containing nitrogen anionic compound, an anionic compound containing a conjugate base of an organic acid with a halogenated hydrocarbon group, and a salt compound obtained by salification with an acidic dye. In addition, if the salt compound contains a polymerizable unsaturated group in a molecule, tolerance is further improved.

[0114] From the viewpoint of color characteristics such as hue, color separation, and color unevenness, the chemical structure of the dye is preferably a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes, and more preferably a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes.

[0115] The dye (A) can be used alone or in combination of two or more.

[0116] The content of the dye (A) in 100% by mass of the nonvolatile components of the photosensitive composition is preferably 0.5% by mass to 80% by mass, and more preferably 1% by mass to 60% by mass.

[0117] (Micronization of organic pigments)

[0118] The organic pigment is preferably used after being micronized. The micronization method is not particularly limited, for example, any one of wet grinding, dry grinding, and dissolution separation can be used. Among these, it is preferred to use a kneader method as a kind of wet grinding for salt milling. The average primary particle size of the micronized pigment obtained by a transmission electron microscope (TEM) is preferably 5nm to 90nm. In addition, from the viewpoint of dispersibility and contrast ratio, the average primary particle size is more preferably 10nm to 70nm.

[0119] For the salt milling treatment, resin may be added as needed. By adding the resin, the pigment is coated with the resin, and stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, synthetic resins modified from natural resins, etc. Among these, it is preferred that the resin is solid at room temperature and insoluble in water, and it is preferred that a part of the resin is soluble in the organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0120] <Alkali-soluble resin (B)>

[0121] The alkali-soluble resin (B) is not limited as long as it is soluble 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. Moreover, the alkali-soluble group possessed by the alkali-soluble resin (B) can be listed, for example, as a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a phenolic hydroxyl group, etc. Among these, a carboxyl group is preferred. In addition, the alkali-soluble resin is preferably a chain-like random polymer. The chain-like includes a branched chain.

[0122] Examples of the alkali-soluble resin (B) include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) 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.

[0123] [Alkali-soluble resin containing polymerizable unsaturated group (B1)]

[0124] The alkali-soluble resin (B1) containing a polymerizable unsaturated group is a resin obtained by imparting a polymerizable unsaturated group to the alkali-soluble resin (B). In the present specification, the alkali-soluble resin containing a polymerizable unsaturated group is preferably a resin synthesized by the following methods (i) and (ii). This further increases the crosslinking density of the film formed by the photosensitive coloring composition by light irradiation, thereby improving the chemical resistance during low-temperature curing.

[0125] [Method (i)]

[0126] Method (i) includes, for example, the following method: first, synthesizing monomers containing epoxy groups and polymers of other monomers, then adding monomers containing monocarboxyl groups to the epoxy groups of the polymers, and reacting the generated hydroxyl groups with polyacid anhydrides to obtain an alkali-soluble resin (B1) containing a polymerizable unsaturated group.

[0127] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidyloxyethyl (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.

[0128] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-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;

[0129] 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 vinyl esters such as vinyl acetate or vinyl propionate, etc.

[0130] In addition, 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-maleimide phenyl) methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrene) maleimide, N-(2,4,6-triphenylene) maleimide, N-(4-chlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine and other N-substituted maleimides, ethylene oxide (ethylene Oxide (EO) modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO) modified (meth) acrylate of phenol, EO or propylene oxide (PO) modified (meth) acrylate of p-cumylphenol, EO modified (meth) acrylate of nonylphenol, PO modified (meth) acrylate of nonylphenol, etc.

[0131] In addition, a phosphoric acid ester group-containing monomer obtained by reacting a phosphating agent such as phosphorus pentoxide or polyphosphoric acid with a hydroxyl group of a hydroxyl group-containing monomer may also be mentioned.

[0132] Examples of the monomer containing a monocarboxyl group include (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and monocarboxylic acids such as (meth)acrylic acid substituted with halogenated alkyl, alkoxy, halogen, nitro, or cyano groups at the α-position.

[0133] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group which does not form an acid anhydride.

[0134] In addition, as a method similar to method (i), for example, the following method can be cited: a monomer containing a monocarboxyl group and a polymer of other monomers are synthesized, and then a monomer containing an epoxy group is added to a part of the carboxyl groups of the polymer to obtain an alkali-soluble resin (B1) containing a polymerizable unsaturated group.

[0135] [Method (ii)]

[0136] Method (ii) includes, for example, a method of synthesizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers to prepare a polymer, and then reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer to synthesize a resin.

[0137] Examples of hydroxyl-containing monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, or polyester mono(meth)acrylates obtained by addition polymerization of polyγ-valerolactone, polyε-caprolactone, and / or poly-12-hydroxystearic acid, etc., can also be cited. Among these, 2-hydroxyethyl (meth)acrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0138] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis(methacryloyloxy)ethyl isocyanate.

[0139] Examples of monomers that can be used other than the above monomers include the other monomers exemplified in the above method (i).

[0140] [Alkali-soluble resin containing no polymerizable unsaturated group (B2)]

[0141] The alkali-soluble resin (B2) not containing a polymerizable unsaturated group may contain a reactive group other than a polymerizable unsaturated group.

[0142] [Blocked isocyanate group-containing alkali-soluble resin (B2-1)]

[0143] The alkali-soluble resin (B) may contain a blocked isocyanate group. A resin containing a blocked isocyanate group has excellent low-temperature curing property and improved chemical resistance.

[0144] 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 formed by protecting the isocyanate group using a compound (hereinafter, also referred to as a blocking agent) that is separated due to heat. The separation temperature of the blocking agent is preferably 70°C to 150°C, and more preferably 80°C to 135°C. The monomer unit containing a blocked isocyanate group can be protected by a blocking agent after the polymerization of the monomer containing a blocked isocyanate group. Alternatively, the isocyanate group of the monomer containing a blocked isocyanate group can be polymerized after protecting the isocyanate group of the monomer containing a blocked isocyanate group.

[0145] Examples of isocyanate group-containing monomers 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, etc. In addition, an equimolar reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0146] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds, and imide compounds. From the viewpoint of protection reaction and deprotection reaction, it is more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0147] Examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, and benzophenone oxime. Among these, methyl ethyl ketone oxime is preferred.

[0148] Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam.

[0149] 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, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred.

[0150] 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.

[0151] Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole.

[0152] Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc. Among these, diethyl malonate is preferred.

[0153] Examples of the pyrazole compound include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole. Among these, 3,5-dimethylpyrazole is preferred.

[0154] Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan.

[0155] Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole.

[0156] Examples of the imide compound include succinimide, maleic acid imide, maleimide, and phthalimide.

[0157] Examples of the urea compound include urea, thiourea, and ethylene urea.

[0158] Examples of the imine compound include ethyleneimine and polyethyleneimine.

[0159] Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

[0160] The blocking agents can be used alone or in combination of two or more.

[0161] Examples of the blocked isocyanate group-containing monomer include the following compounds, but the present invention is not limited thereto.

[0162] [Chemistry 15]

[0163]

[0164] Examples of commercially available blocked isocyanate group-containing monomers include Karenz MOI-DEM (blocking agent desorption temperature: 85° C. to 95° C.), MOI-BP (blocking agent desorption temperature: 105° C. to 115° C.), and MOI-BM (125° C. to 135° C.), all manufactured by Showa Denko K.K.

[0165] From the viewpoint of storage stability and chemical resistance during low-temperature curing, the content of the blocked isocyanate group-containing monomer units in all structural units of the alkali-soluble resin (B) is preferably 1 to 50 mol %, more preferably 5 to 40 mol %.

[0166] 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 still more preferably 5,000 to 25,000. The value of Mw / Mn (number average molecular weight) is preferably 10 or less.

[0167] The acid value of the alkali-soluble resin (B) is preferably 20 mgKOH / g to 200 mgKOH / g, more preferably 30 mgKOH / g to 180 mgKOH / g.

[0168] The alkali-soluble resin (B) can be used alone or in combination of two or more.

[0169] The content of the alkali-soluble resin (B) is preferably 20 to 400 parts by mass, more preferably 30 to 250 parts by mass, based on 100 parts by mass of the dye (A).

[0170] <Polymerizable compound (C)>

[0171] Examples of the polymerizable compound (C) include monomers or oligomers having a polymerizable unsaturated group. Examples of the polymerizable compound (C) include polymerizable compounds having an acid group, polymerizable compounds having a urethane bond, and other polymerizable compounds.

[0172] (Polymerizable compound having an acid group)

[0173] When the photosensitive composition of the present invention contains a polymerizable compound having an acid group, the solubility of the coating film in the alkaline developer during alkaline development is improved, thereby increasing the development speed and suppressing the residue. Examples of the acid group include sulfonic acid group, carboxyl group, phosphoric acid group, and the like.

[0174] Examples of the polymerizable compound having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyols and (meth)acrylic acid and dicarboxylic acids; and esters of polycarboxylic acids and monohydroxyalkyl (meth)acrylates. For example, there can be mentioned free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; 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, and benzene-1,3,5-tricarboxylic acid with monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0175] Examples of commercially available products include Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd. and Aronix M-5300, M-5400, M-5700, M-510, and M-520 manufactured by Toagosei Co., Ltd.

[0176] (Polymerizable compound having urethane bond)

[0177] The photosensitive coloring composition of the present invention can suppress the precipitation of the coloring material when the coating film is heated by containing the photopolymerizable compound having a urethane bond, and can also improve the chemical resistance and the adhesion to the substrate.

[0178] Examples of the polymerizable compound having a urethane bond include polyfunctional urethane acrylates obtained by reacting polyfunctional isocyanate with (meth)acrylate having a hydroxyl group, and polyfunctional urethane acrylates obtained by reacting polyfunctional isocyanate with alcohol and then with (meth)acrylate having a hydroxyl group.

[0179] Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, di-trimethylolpropane 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, a reaction product of an epoxy group-containing compound and a carboxyl (meth)acrylate, and a hydroxyl-containing polyol polyacrylate.

[0180] Moreover, as a polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc. are mentioned.

[0181] Commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., and UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0182] 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, di-trimethylolpropane tetra(meth)acrylate, various acrylates and methacrylates such as (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, tricyclodecyl (meth)acrylate, (meth)acrylate of hydroxymethylated melamine, epoxy (meth)acrylate, urethane acrylate, (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, etc.

[0183] Commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120 manufactured by Nippon Kayaku Co., Ltd. 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, Viscoat #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.

[0184] The polymerizable compound can be used alone or in combination of two or more.

[0185] The amount of the polymerizable compound (C) added is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 40% by mass, in 100% by mass of the nonvolatile component of the photosensitive coloring composition.

[0186] [Polymerization initiator (D)]

[0187] The polymerization initiator (D) contains peroxy triazine (D1). Peroxy triazine (D1) contains one or more of peroxy triazine (D1a) represented by general formula (1a) and peroxy triazine (D1b) represented by general formula (1b). Peroxy triazine (D1a) represented by general formula (1a) or peroxy triazine (D1b) represented by general formula (1b) has both photopolymerization properties that can efficiently absorb light of a wavelength of 365 nm or the like emitted from a high-pressure mercury lamp or LED lamp to generate free radicals, and thermal polymerization properties that can generate free radicals by heat, and can generate free radicals even in a low-temperature heating process. In addition, peroxy triazine (D1a) represented by general formula (1a) and peroxy triazine (D1b) represented by general formula (1b) can be used in combination.

[0188] [Triazine peroxide (D1a)]

[0189] The peroxytriazine (D1a) (hereinafter referred to as peroxytriazine (D1a)) represented by the general formula (1a) is the following compound.

[0190] General formula (1a)

[0191] [Chemistry 16]

[0192]

[0193] In the general formula (1a), R 1 and R 3 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, n represents an integer from 0 to 2, and X is a group containing an aromatic ring, preferably the general formula (2a): Ar 1 ,Ar 2 ,Ar 3 , or Ar 4 The aryl group represented by

[0194] In the general formula (1a), R 1 and R 3 R is independently a methyl group or an ethyl group. From the viewpoint that the storage stability of the polymerizable composition is improved due to the high decomposition temperature of the peroxytriazine, 1 and R 3 Preferred is methyl.

[0195] In the general formula (1a), R 2 It is 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 a straight chain or a branched chain. 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 peroxytriazine, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferred. The peroxytriazine has a high decomposition temperature, so the storage stability of the polymerizable composition is increased, and the sensitivity to the light of the lamp is high. In this regard, a methyl group and an ethyl group are more preferred.

[0196] n in the general formula (1a) is represented by an integer of 0 to 2. From the viewpoint of easy synthesis of the peroxytriazine, 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 , thereby efficiently absorbing the light of the lamp and reducing the yellowness of the cured product, which is more preferable from this point of view.

[0197] General formula (2a)

[0198] [Chemistry 17]

[0199]

[0200] In the general formula (2a), m represents an integer from 0 to 3, and R 4 is an independent substituent, representing an alkyl group having 1 to 18 carbon atoms, general formula (3a): R 5 -Y-, a nitro group, or a cyano group, wherein Y represents an oxygen atom or a sulfur atom, and R 5 represents a hydrocarbon group having 1 to 18 carbon atoms which may have at least one of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or -CO-R. 4 It is represented by two adjacent general formulas (3a): R 5 The above 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.

[0201] In the general formula (2a), m is represented by an integer of 0 to 3. From the viewpoint of easy synthesis of the peroxytriazine, m is preferably 0 to 2, and from the viewpoint of efficiently absorbing light from a lamp, m is more preferably 1.

[0202] From the perspective of efficiently absorbing the light of the lamp, the R 4 Preferably, the independent substituent represents an alkyl group having 1 to 8 carbon atoms, or the general formula (3a): R 5 -Y-, wherein 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 in the carbon skeleton and a hydroxyl group at the terminal, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or R 4 By connecting two adjacent general formula (3a): R 5 -Y- to form a 5- to 6-membered hydrocarbon group.

[0203] The R 4For example, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, octyl, 2-ethylhexyl, dodecyl, and octadecyl may be mentioned; methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, octyloxy, 2-ethylhexyloxy, dodecyloxy, octadecyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-(2-hydroxyethoxy)ethoxy, 2-(2-ethoxyethoxy)ethoxy, The functional groups of the present invention include alkoxy groups such as 2-(4-hydroxy-1-propyl)ethoxy, 3-hydroxy-n-propyloxy, 3-methoxy-n-propyloxy, 1,2-dihydroxypropyloxy, methylenedioxy, dimethylmethylenedioxy, and ethylenedioxy; aryloxy groups such as phenyloxy and 4-isopropylphenyloxy; alkylthio groups such as methylthio, ethylthio, hexylthio, 2-methoxyethylthio, and 2-(2-methoxyethoxy)ethylthio; arylthio groups such as phenylthio, 2-methylphenylthio, and 4-methylphenylthio; acyl groups such as acetyl, n-butyryl, 2-ethylhexanoyl, benzoyl, and 2-methylbenzoyl. Compounds represented by the general formula (1a) having these functional groups are preferred because they have a high absorbance at a wavelength of 365 nm and absorb light from a lamp efficiently.

[0204] Furthermore, among these, the peroxytriazine (D1a) is preferred from the viewpoints of high solubility in the polymerizable composition, easy synthesis, and high sensitivity to light from a lamp. 1 More preferred is methyl.

[0205] The R 4 The substitution position is not particularly limited. When X is Ar 1 In the case of 4 At least one of the bonds is connected to the para position of the triazine group, and when X is Ar 2 In the case of 4 At least one of the following is bonded to the 4-position of the benzene ring that is not bonded to the triazine group, and when X is Ar 3 In the case of 4 At least one of them is bonded to the 4-position of the naphthalene ring, and when X is Ar 4 In the case of R 4 It is preferred that at least one of the groups is bonded to the 4-position of the benzene ring that is not bonded to the triazine group because it efficiently absorbs light from a lamp.

[0206] The following are examples of peroxytriazine (D1a), but are not limited to these.

[0207] [Chemistry 18]

[0208]

[0209] [Chemistry 19]

[0210]

[0211] [Chemistry 20]

[0212]

[0213] The content of the triazine peroxide (D1a) in the nonvolatile component of the photosensitive composition is preferably 0.5% by mass to 7% by mass, more preferably 1% by mass to 3% by mass.

[0214] [Triazine peroxide (D1b)]

[0215] The peroxytriazine (D1b) (hereinafter referred to as peroxytriazine (D1b)) represented by the general formula (1b) is the following compound.

[0216] General formula (1b)

[0217] [Chemistry 21]

[0218]

[0219] 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 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, -CO-R, -YR, or -N-RR', Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, 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 is a group containing an aromatic ring, and is preferably of the following general formula (2b): Ar 1 ,Ar 2 , or Ar 3 The aryl group represented by

[0220] General formula (2b)

[0221] [Chemistry 22]

[0222]

[0223] In the general formula (2b), m represents an integer from 0 to 3, and R 11is an independent substituent, which is a substitutable aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substitutable aromatic hydrocarbon group having 6 to 20 carbon atoms, a substitutable heterocyclic group having 2 to 20 carbon atoms, -CO-R, -YR, or -N-RR', wherein Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, a substitutable aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substitutable aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substitutable heterocyclic group having 2 to 20 carbon atoms.

[0224] In the general formula (1b), R 1 and R 2 Each independently represents a methyl group or an ethyl group, and a methyl group is preferred from the viewpoint that the decomposition temperature is high and the storage stability of the polymerizable composition is improved.

[0225] In the 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 a linear chain or a branched chain. 3 For example, methyl, ethyl, propyl, 2,2-dimethylpropyl, phenyl, isopropylphenyl, etc. are mentioned. Among these, methyl, ethyl, propyl, 2,2-dimethylpropyl, and phenyl are preferred from the viewpoint of easy synthesis of the peroxytriazine derivative. The peroxytriazine derivative has a high decomposition temperature, so the storage stability of the polymerizable composition is improved, and the sensitivity to light is high. From this point of view, methyl and ethyl are more preferred.

[0226] In the general formula (1b), R 4 is a substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -YR, or -N-RR', wherein Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, a substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substituted heterocyclic group having 2 to 20 carbon atoms. 4 The effect on the absorption wavelength of peroxytriazine derivatives is small, so even if R 4 In the above wide range, good sensitivity is also shown. In addition, the "substituent" in the "may be substituted" includes halogen atoms, aliphatic hydrocarbon groups that may have ether bonds or thioether bonds in the carbon skeleton, aromatic hydrocarbon groups, heterocyclic groups, acyl groups, cyano groups, nitro groups, carboxyl groups, epoxy groups, hydroxyl groups, etc. From the perspective of high stability, the R 4Preferred are a substitutable aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substitutable aromatic hydrocarbon group having 6 to 20 carbon atoms, a substitutable heterocyclic group having 2 to 20 carbon atoms, -CO-R, or -YR. From the viewpoint of easy synthesis, -CO-R is more preferred, wherein R is a substitutable aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substitutable aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substitutable heterocyclic group having 2 to 20 carbon atoms.

[0227] In the general formula (2b), m represents an integer of 0 to 3, and m is preferably 0 to 2 from the viewpoint of easy synthesis, and more preferably 1 from the viewpoint of efficient light absorption.

[0228] In the general formula (2b), R 11 is a substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a substituted heterocyclic group having 2 to 20 carbon atoms, -CO-R, -YR, or -N-RR', wherein Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, a substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substituted heterocyclic group having 2 to 20 carbon atoms. 11 The effect on the absorption wavelength of peroxytriazine derivatives is small, so even if R 11 In the above wide range, good sensitivity is also shown. In addition, the "substituent" in the "may be substituted" includes halogen atoms, aliphatic hydrocarbon groups that may have ether bonds or thioether bonds in the carbon skeleton, aromatic hydrocarbon groups, heterocyclic groups, acyl groups, cyano groups, nitro groups, carboxyl groups, epoxy groups, hydroxyl groups, etc. The R 11 is an independent substituent, representing an alkyl group having 1 to 20 carbon atoms, general formula (3b): R 12 -Y-, a nitro group, or a cyano group, wherein Y represents an oxygen atom or a sulfur atom, and R 12 It may be a hydrocarbon group having 1 to 20 carbon atoms which may have at least one of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have an alkyl group, or -CO-R. 11 It can be obtained by connecting two adjacent general formulas (3b): R 12 -Y- to form a 5- to 6-membered ring.

[0229] Specific examples of the peroxytriazine (D1b) of the present invention are shown below, but the present invention is not limited to these.

[0230] [Chemistry 23]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236] In the present invention, 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, and compound 81b.

[0237] The content of the triazine peroxide (D1b) in the nonvolatile component of the photosensitive composition is preferably 0.5% by mass to 7% by mass, more preferably 1% by mass to 3% by mass.

[0238] [Oxime ester initiator (D2)]

[0239] The polymerization initiator (D) may further contain an oxime ester initiator (D2) (hereinafter, also referred to as initiator (D2)). The initiator (D2) causes the cleavage of the NO bond of the oxime by absorbing ultraviolet rays, generating imino radicals and alkoxy radicals. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small exposure amount. Therefore, even when the pigment concentration of the photosensitive coloring composition is high, the initiator (D2) will not reduce the curability of the coating film. The initiator (D2) is preferably propylene glycol monomethyl ether acetate. The extinction coefficient of light at a wavelength of 365nm is 5.0×10 3 Oxime ester compounds having a concentration of L / mol·cm or more are used. This allows the photopolymerization reaction to proceed sufficiently even under low exposure conditions, thereby not only forming a film having excellent adhesion but also improving film productivity.

[0240] Examples of the initiator (D2) include compounds represented by the following general formulae (D21) to (D25).

[0241] (Oxime ester photopolymerization initiator (D21) represented by general formula (D21))

[0242] General formula (D21)

[0243] [Chemistry 24]

[0244]

[0245] In the general formula (D21), R 1 and R 2 R 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. 3 Indicates -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 sulfone group. 5 represents a phenyl group which may have a substituent. 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. 1 ~R 4 The alkyl group, cyclic alkyl group, acyl group, and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and a phenyl group. 1 ~R 4 The hydrogen atoms of the substituents in the 6 Replace. 6 It represents a halogen atom, a fluorine atom, an alkyl group, a cyclic alkyl group, an acyl group, a nitro group, a sulfone group, and a phenyl group.

[0246] Examples of the oxime ester photopolymerization initiator (D21) represented by the general formula (D21) include 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9 .H.-carbazol-3-yl〕-ethane-1-one oxime-O-benzoate, ethyl ketone, 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-, 1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-〔9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl〕-, 1-(O-acetyl oxime), ethyl ketone, 1-〔9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl〕-, 1-(O-acetyl oxime), ethyl ketone, 1-〔9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl〕 =Hydrofuranylbenzoyl)-9H-carbazol-3-yl〕-, 1-(O-acetyl oxime), ethyl ketone, 1-〔9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl〕-, 1-(O-acetyl oxime), ethyl ketone, 1-〔9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)benzoyl}-9H-carbazol-3-yl〕-, 1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-〔9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl〕-, 1-(O-acetyl oxime), ethyl ketone, 1-〔9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl) =The compounds represented by chemical formula (D21-1) to chemical formula (D21-9) are 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), and compounds represented by chemical formula (D21-1) to chemical formula (D21-9) below.

[0247] [Chemistry 25]

[0248]

[0249] (Oxime ester photopolymerization initiator (D22) represented by general formula (D22)) General formula (D22)

[0250] [Chemistry 26]

[0251]

[0252] In the general formula (D22), R 1 and R 2 R 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 which may have a substituent, or a phenyl group. 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 sulfone group. 1 ~R 3 The alkyl group, cyclic alkyl group, acyl group, and phenyl group in R may be substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and a phenyl group. 4 R is a hydrogen atom, a linear or branched 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. 4 The hydrogen atoms of the aryl group or arylalkyl group represented by R 21 、-OR 21 、-COR 21 , hydroxyl, nitro, cyano, halogen atom, or COOR 21 Replacement, R 21 represents 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, aryl, and arylalkyl groups represented may be further substituted with hydroxyl, nitro, cyano, halogen atoms, or carboxyl groups. The alkyl, acyl, and phenyl groups may be substituted with substituents selected from the group consisting of halogen atoms, alkoxy groups having 1 to 10 carbon atoms, and phenyl groups. 1 ~R 4 The hydrogen atom of the substituent in may be further substituted by another substituent.

[0253] In the general formula (D22), R 1 ~R 4Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0254] In the general formula (D22), R 1 ~R 4 Examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclododecyl.

[0255] In the general formula (D22), R 4 , R 21 Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthracenyl, and the like.

[0256] In the general formula (D22), R 4 Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0257] Examples of the oxime ester photopolymerization initiator (D22) represented by the general formula (D22) include compounds represented by the following chemical formulas (D22-1) to (D22-10).

[0258] [Chemistry 27]

[0259]

[0260]

[0261]

[0262] (Oxime ester photopolymerization initiator (D23) represented by general formula (D23))

[0263] General formula (D23)

[0264] [Chemistry 28]

[0265]

[0266] In the general formula (D23), R 1 and R 2R 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. 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 sulfone group. 1 ~R 3 The alkyl group, acyl group, and phenyl group in R may be substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and a phenyl group. 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. 1 ~R 6 The hydrogen atom of the substituent in may be further substituted by another substituent.

[0267] In the general formula (D23), R 1 ~R 5 Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0268] In the general formula (D23), R 1 ~R 5 Examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclododecyl.

[0269] In the general formula (D23), R 4 and R 6 Examples of the heterocyclic group having 4 to 20 carbon atoms include 5-membered to 7-membered heterocyclic rings such as benzofuran, isobenzofuran, pyridyl, pyrimidyl, furanyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazolidinyl, oxazolidinyl, isoxazolidinyl, piperidinyl, piperazinyl and morpholinyl.

[0270] In the general formula (D23), R 6Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthracenyl, and the like.

[0271] In the general formula (D23), R 6 Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0272] Examples of the oxime ester photopolymerization initiator (D23) represented by the general formula (D23) include compounds represented by the following chemical formulas (D23-1) to (D23-3).

[0273] [Chemistry 29]

[0274]

[0275] (Oxime ester photopolymerization initiator (D24) represented by general formula (D24))

[0276] General formula (D24)

[0277] [Chemistry 30]

[0278]

[0279] In the general formula (D24), R 1 and R 2 R 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. 3 , R 5 R 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. 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 alkyl group, acyl group, and phenyl group may be substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and a phenyl group. 1 ~R 5 The hydrogen atom of the substituent in may be further substituted by another substituent.

[0280] In the general formula (D24), R 1 ~R 5Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0281] As R in the general formula (D24) 1 , R 2 , R 3 and R 5 Examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclododecyl.

[0282] Examples of the oxime ester photopolymerization initiator (D24) represented by the general formula (D24) include 1,2-heptanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), 1,2-octanedione, 1-[4-(benzoyl)phenyl]-, 2-(O-benzoyl oxime), ethyl ketone, 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).

[0283] [Chemistry 31]

[0284]

[0285]

[0286] (Oxime ester photopolymerization initiator (D25) represented by general formula (D25))

[0287] General formula (D25)

[0288] [Chemistry 32]

[0289]

[0290] In the general formula (D25), R1 and R2 each independently represent 11 or COR 11 ,

[0291] 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, and R 11 The alkyl, aryl, arylalkyl or alkyl portion of the heterocyclic group represented may have a branched side chain or may be a cyclic alkyl group.

[0292] 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 group, aryl group, arylalkyl group, or alkyl group of the heterocyclic group represented by R3 may have a branched side chain or may be a cyclic alkyl group. The hydrogen atom of the aryl group, arylalkyl group, or heterocyclic group represented by R3 may be further substituted by 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 , hydroxyl, nitro, cyano, halogen atom, or COOR 21 replace,

[0293] 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 23The hydrogen atoms of the alkyl, aryl, arylalkyl or heterocyclic group represented by R may be further substituted by a hydroxyl group, a nitro group, a cyano group, a halogen atom or a carboxyl group. 21 , R 22 and R 23 The alkyl, aryl, arylalkyl or alkylene portion of the heterocyclic group represented may be replaced by -O-, -S-, -COO-, -OCO-, -NR- 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or CSO- are interrupted once to five times,

[0294] 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 R 24 The alkyl, aryl, arylalkyl or alkyl portion of the heterocyclic group represented may have a branched side chain or may be a cyclic alkyl group.

[0295] R4 represents a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, or a halogen atom, and n represents 0 or 1.

[0296] In the general formula (D25), R3, R 11 , R 21 , R 22 , R 23 and R 24 Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0297] In the general formula (D25), R3, R 11 , R 21 , R 22 , R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, phenyl substituted with one or more of the alkyl groups, biphenyl, naphthyl, anthracenyl, and the like.

[0298] In the general formula (D25), R3, R 11 , R 21 , R22 , R 23 and R 24 Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0299] In the general formula (D25), R3, R 11 , R 21 , R 22 , R 23 and R 24 Examples of the heterocyclic group having 2 to 20 carbon atoms include 5- to 7-membered heterocyclic rings such as pyridyl, pyrimidinyl, furanyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazolidinyl, oxazolidinyl, isoxazolidinyl, piperidinyl, piperazinyl and morpholinyl.

[0300] The method for producing the oxime ester photopolymerization initiator (D25) represented by the general formula (D25) is not particularly limited, and a conventional method can be used. For example, the method described in International Publication No. 2015 / 152153 can be used.

[0301] Examples of the oxime ester photopolymerization initiator (D25) represented by the general formula (D25) include compounds represented by the following chemical formulas (D25-1) to (D25-8).

[0302] [Chemistry 33]

[0303]

[0304]

[0305] Among these oxime ester photopolymerization initiators, preferred are 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), and ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3-yl]-, 1-(O-acetyl oxime).

[0306] Commercially available products include: 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), IRGACURE OXE-03, and IRGACURE OXE-04 manufactured by BASF, N-1919, NCI-730, NCI-831, and 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, and TRONLY TR-PBG-3054 manufactured by Changzhou Qiangli New Materials Co., Ltd. Among these, from the viewpoint of pattern formability and substrate adhesion, TRONLY TR-PBG-345, NCI-730, and NCI-930 are more preferred, and IRGACURE OXE-04 and NCI-831 are further preferred.

[0307] The content of the oxime ester initiator (D2) in the nonvolatile component of the photosensitive composition is preferably 0.5% by mass to 4% by mass, more preferably 1% by mass to 2% by mass.

[0308] [Other polymerization initiators (D3)]

[0309] The polymerization initiator (D) may contain other polymerization initiators (D3) other than those mentioned above. Examples of other polymerization initiators (D3) include acetophenone compounds such as 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone; and benzophenone. Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone compounds such as benzoylbenzoic acid, benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)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-phenylvinyl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxy)- triazine compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), or ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) and other oxime ester compounds; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate ester compounds; carbazole compounds; imidazole compounds; or titanocene compounds, etc.

[0310] As for commercial products of other polymerization initiators (D3), as acetophenone compounds, there can be mentioned "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone), all of which are manufactured by IGM Resins. As phosphine compounds, there can be mentioned all of which are manufactured by IGM Resins. Resins Co., Ltd., "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) and "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide).

[0311] The polymerization initiator (D) can be used alone or in combination of two or more.

[0312] From the viewpoint of adhesion, line width, and chemical resistance during low-temperature curing, the content of the polymerization initiator (D) in the nonvolatile component of the photosensitive composition is preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, and even more preferably 1% by mass to 5% by mass.

[0313] From the viewpoint of chemical resistance, the content of the peroxytriazine (D1) in the nonvolatile component of the photosensitive composition 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.

[0314] The mass ratio of the peroxytriazine (D1) to the oxime ester 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.

[0315] The peroxytriazine (D1) is preferably the peroxytriazine (D1b) from the viewpoint of storage stability and the fact that the line width of the pattern is less likely to become thick.

[0316] [Thermosetting compound (E)]

[0317] The photosensitive composition of the present invention may contain a thermosetting compound (E). Thus, the thermosetting compound (E) reacts through the heating process, and the crosslinking density is increased, thereby improving the heat resistance of the film. The thermosetting compound (E) is a compound having a thermosetting group and no ethylenically unsaturated double bond.

[0318] Examples of the thermosetting compound (E) include epoxy compounds, oxetane compounds, blocked isocyanate 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.

[0319] (Epoxy compound (E1))

[0320] Examples of the epoxy compound (E1) include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isopentane, etc.); Polymers of phenols and aromatic dimethylols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyledimethanol, α,α,α',α'-biphenyledimethanol, etc.); polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates of bisphenols and various aldehydes; glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, etc. obtained by glycidylating alcohols, etc.

[0321] Examples of commercially available products include: EPICOAT 807, EPICOAT 815, EPICOAT 825, EPICOAT 827, EPICOAT 828, EPICOAT 190P, EPICOAT 191P manufactured by Shell Oil Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, EPPN-501H, and EPP manufactured by Nippon Kayaku Co., Ltd. N-502H, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EPICOAT 1004, EPICOAT 1256, JER1032H60, JER157S65, JER157S70, JER152, JER154, CELLOXIDE 2021, EHPE-3150, Nagase Chemical Co., Ltd. DENACOL EX-211, DENACOL EX-212, DENACOL EX-252, DENACOL EX-313, DENACOL EX-314, DENACOL EX-321, DENACOL EX-411, DENACOL EX-421, DENACOL EX-51 ... DENACOL EX-521, DENACOL EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-614B, DENACOL EX-622, DENACOL EX-711, DENACOL EX-721, TEPIC-L, TEPIC-H, TEPIC-S manufactured by Nissan Chemical Industries, Ltd., etc.

[0322] The epoxy compound (E1) is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0323] The epoxy equivalent of the epoxy compound (E1) is preferably 50 g / eq to 400 g / eq, more preferably 100 g / eq to 200 g / eq. The epoxy equivalent is defined as the mass of the epoxy compound containing 1 equivalent of epoxy groups.

[0324] From the viewpoint of chemical resistance after low-temperature heating, the epoxy compound (E1) more preferably includes a compound represented by the following general formula (110).

[0325] General formula (110)

[0326] [Chemistry 34]

[0327]

[0328] In the general formula (110), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0329] R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol.

[0330] The group formed by removing m hydroxyl groups from an m-valent alcohol is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, cyclic, or a group formed by bonding these groups. Examples of the alkyl group having 2 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, 2,2-dimethylpropyl, butyl, isobutyl, tert-butyl, 3,3-dimethylbutyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl. Among these, branched alkyl groups having 3 to 12 carbon atoms are more preferred.

[0331] m represents an integer of 1-6, and n represents an integer of 1-30.

[0332] When m is 2 or more, n in each bracketed group in the general formula (110) may be the same or different.

[0333] Examples of the compound represented by the general formula (110) include 1,2-epoxy-4-(2-oxacyclopropyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0334] From the viewpoint of chemical resistance during low-temperature curing, the content of the epoxy compound (E1) in 100% by mass of the nonvolatile component of the photosensitive composition is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 5% by mass to 15% by mass.

[0335] (Oxetane compound (E2))

[0336] The oxetane compound (E2) is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0337] Examples of the monofunctional oxetane compound include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-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, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0338] Examples of commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

[0339] 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 -oxetanyl methyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanyl methyl) ether, triethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, 1,4-bis(3-ethyl-3-oxetanyl methoxy) butane, 1,6-bis(3-ethyl-3-oxetanyl methoxy) hexane, polyethylene glycol bis(3-ethyl-3-oxetanyl methoxy) ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanyl methyl) ether, and the like.

[0340] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0341] Examples of trifunctional or higher-functional oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetra(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetra(3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, A polymer obtained by free radical polymerization of a (meth)acrylic monomer such as OXE-30, for example, oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462, or di-trimethylolpropane tetra(3-ethyl-3-oxetanemethyl)ether, or oxetane-containing resin (e.g., oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), or the like.

[0342] The content of the oxetane compound (E2) in 100% by mass of the nonvolatile components of the photosensitive composition is preferably from 0.5% by mass to 50% by mass, and more preferably from 1% by mass to 40% by mass.

[0343] (Blocked isocyanate compound (E3))

[0344] The blocked isocyanate compound (E3) is a compound having a blocked isocyanate group obtained by protecting the isocyanate group with a blocking agent described below. The blocked isocyanate compound (E3) does not contain an alkali-soluble group.

[0345] The blocking agent may be the above-mentioned compounds. 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, thiol 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 under low-temperature curing, active methylene compounds are particularly preferred. The desorption temperature of the active methylene compound or the temperature of the transesterification reaction is as low as 80°C to 110°C, and the active methylene compound reacts sufficiently even under low-temperature heating, thereby improving tolerance.

[0346] Examples of the compound having an isocyanate group include compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylidene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate;

[0347] Compounds having an alicyclic structure such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanate methyl)cyclohexane;

[0348] Compounds having an aromatic structure such as 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane 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, toluene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene. In addition, biuret forms, isocyanurate forms, adduct forms, allophanate forms of these compounds, and reaction products of these compounds with polyols, etc. can be mentioned.

[0349] From the viewpoint of chemical resistance during low-temperature curing, the compound having an isocyanate group is preferably a biuret form, isocyanurate form, adduct form, or allophanate form of a compound having an aliphatic structure or a compound having an alicyclic structure. Among them, a biuret form of hexamethylene diisocyanate blocked with an active methylene compound is more preferred, and an isocyanurate form of hexamethylene diisocyanate blocked with an active methylene compound is particularly preferred.

[0350] The content of the blocked isocyanate compound (E3) in 100% by mass of the nonvolatile component of the photosensitive composition is preferably 0.05% by mass to 50% by mass, more preferably 0.1% by mass to 40% by mass, particularly preferably 5% by mass to 15% by mass.

[0351] The thermosetting compound (E) may be used alone or in combination of two or more. In particular, from the viewpoint of chemical resistance during low-temperature curing, the thermosetting compound (E) is preferably a combination of an epoxy compound (E1) and a blocked isocyanate compound (E3).

[0352] From the viewpoint of chemical resistance under low-temperature curing, the content of the thermosetting compound (E) in 100% by mass of the non-volatile component of the photosensitive composition is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 5% by mass to 15% by mass.

[0353] [Ultraviolet absorber (F)]

[0354] The photosensitive composition of the present invention may contain an ultraviolet absorber (F).

[0355] The ultraviolet absorber (F) is a compound having an ultraviolet absorbing function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0356] The content of the ultraviolet absorber (F) in the nonvolatile component of the photosensitive composition is preferably 1% to 5% by mass, more preferably 1% to 3% by mass, and preferably 5% to 70% by mass in 100% by mass of the total of the polymerization initiator (D) and the ultraviolet absorber (F).

[0357] [Leveling agent (L)]

[0358] The photosensitive composition of the present invention may contain a leveling agent (L). As a result, the wettability and drying properties of the substrate during coating are further improved. Examples of the leveling agent (L) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0359] Examples of the silicon-based surfactant include linear polymers containing a siloxane bond and modified siloxane polymers having an organic group introduced into a side chain or a terminal.

[0360] Examples of commercially available products include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-335N, BYK-336, BYK-337, BYK-338, BYK-339, BYK-340, BYK-341, BYK-342, BYK-343, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-350, BYK-351, BYK-352, BYK-353, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-360, BYK-361, BYK-363, BYK-364, BYK-365 3. BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray FZ-7002, FZ-2110, FZ-2122, FZ-2123, FZ-2191, FZ-5609 manufactured by Dow Corning, X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0361] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain.

[0362] Examples of commercially available products include Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-611, Surflon S-651, and Surflon S-386 manufactured by AGC Seimi Chemical Co., Ltd., and Megafac F-253, Megafac F-477, Megafac F-551, Megafac F-552, Megafac F-555, Megafac F-558, and Megafac F-560 manufactured by DIC Corporation. Megafac F-560, Megafac F-570, Megafac F-575, Megafac F-576, Megafac R-40-LM, Megafac R-41, Megafac RS-72-K, Megafac DS-21, FC-4430 and FC-4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1 and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals, and Ftergent 602A manufactured by NEOS.

[0363] The leveling agent (L) can be used alone or in combination of two or more.

[0364] The content of the leveling agent (L) in 100% by mass of the nonvolatile components of the photosensitive composition is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass. Within the above range, the balance between the coating properties and the adhesion of the photosensitive composition is further improved.

[0365] [Pigment derivatives (N)]

[0366] The photosensitive composition of the present invention may contain a pigment derivative (N).

[0367] Pigment derivative (N) is a dispersing aid, and examples thereof include compounds having a structure in which a portion of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. Pigment derivative (N) includes, for example, compounds having acidic substituents such as sulfonic groups, carboxyl groups, and phosphoric acid groups, and amine salts thereof, compounds having a sulfonamide group or having a basic substituent such as a tertiary amino group at the end, and compounds having a neutral substituent such as a phenyl group or a phthalimide alkyl group.

[0368] Examples of the pigment derivatives include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzisoindole compounds, isoindolinone compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, reducing compounds, and naphthalocyanine compounds.

[0369] The pigment derivative (N) can be used alone or in combination of two or more.

[0370] [Organic solvent (O)]

[0371] The photosensitive composition of the present invention may contain an organic solvent (O).

[0372] 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-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-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-diethyl Benzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotert-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 propylene 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, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc. Among these, 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, or ketones such as cyclohexanone are preferred from the viewpoint of the dispersibility of the pigment and the solubility of the alkali-soluble resin.

[0373] The organic solvent (O) can be used alone or in combination of two or more.

[0374] [Acidic resin type dispersant (S)]

[0375] The photosensitive composition of the present invention contains an acidic resin dispersant (S). The acidic resin dispersant (S) can use an existing resin dispersant. The acidic resin dispersant (S) has a colorant affinity site adsorbed on the pigment (A) and a relaxation site that has high affinity with components other than the pigment (A) and causes steric repulsion between dispersed particles. The colorant affinity site adsorbed on the pigment (A) is preferably a comb-shaped structure or an AB block structure.

[0376] Examples of the acidic resin dispersant (S) include: carbamate dispersants such as polyurethane; polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylates, polysiloxanes, hydroxyl-containing polycarboxylates, or modified products thereof; amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphates, etc. In addition, the acidic resin dispersant (S) does not contain the monomer containing the blocked isocyanate group.

[0377] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, it is preferable to use a resin dispersant having a carboxyl group. Examples of the resin dispersant having a carboxyl group include a comb-shaped resin dispersant and a linear resin dispersant.

[0378] [Comb-shaped resin dispersant having a carboxyl group]

[0379] The comb-shaped resin dispersant having a carboxyl group is, for example, a resin dispersant obtained by reacting a hydroxyl group of a polymer having a hydroxyl group with an anhydride group of a tetracarboxylic dianhydride; or a resin dispersant obtained by polymerizing monomers in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group with an anhydride group of a tetracarboxylic dianhydride; or a resin dispersant having a side chain obtained by polymerizing monomers having a hydroxyl group, a tert-butyl group or an oxetane skeleton, a blocked isocyanate or other thermal crosslinking group, or other monomers in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group with an anhydride group of a tetracarboxylic dianhydride; and a resin dispersant obtained by reacting an ethylenically unsaturated monomer having an isocyanate group with the hydroxyl group of the side chain. The comb-shaped resin 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 of a polymer as a monomer in the side chain.

[0380] [Linear-chain resin dispersant having a carboxyl group]

[0381] The linear resin dispersant having a carboxyl group can be produced, for example, by using a vinyl polymer having a hydroxyl group at one end as a raw material and adding tricarboxylic anhydride to the hydroxyl group. The linear resin dispersant having a carboxyl group can also be said to be a vinyl polymer having an aromatic carboxyl group at the end.

[0382] The acidic resin dispersants (S) can be used alone or in combination of two or more.

[0383] The photosensitive composition of the present invention may further contain a polymer dispersant having a basic functional group. Examples of the polymer dispersant having a basic functional group include a nitrogen-containing graft copolymer, a nitrogen-containing acrylic block copolymer having a tertiary amino group, a quaternary ammonium salt group, a nitrogen-containing heterocyclic ring or the like in a side chain, or a urethane polymer dispersant.

[0384] The amount of the acidic resin dispersant (S) used is preferably about 3% to 200% by mass, more preferably about 5% to 100% by mass, relative to the pigment (A). If used in an appropriate amount, film-forming properties are improved.

[0385] [Method for producing photosensitive composition]

[0386] In the photosensitive composition of the present invention, for example, a pigment (A), an acidic resin dispersant (S), an alkali-soluble resin (B), an organic solvent (O), etc. are added for dispersion treatment to produce a dispersion. Thereafter, a polymerizable compound (C) and a polymerization initiator (D) are mixed in the dispersion to produce the photosensitive composition of the present invention. In addition, the timing of mixing each material is arbitrary. In addition, multiple dispersion steps may be performed.

[0387] Examples of the disperser for performing the dispersion treatment include a double roll mill, a triple roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0388] The average dispersed particle size (secondary particle size) of the dye (A) is preferably 30 nm to 200 nm, more preferably 40 nm to 200 nm. When the particle size is appropriate, a photosensitive composition having high dispersion stability can be easily obtained.

[0389] In the determination method of average dispersed particle diameter (secondary particle diameter), for example, using the microtrack UPA-EX150 of Nikkiso Co., Ltd. using dynamic light scattering method (fast Fourier transform (fast Fourier transform, FFT) power spectrum method), particle permeability is set to absorption mode, particle shape is set to non-spherical, and D50 particle diameter is set to average diameter. The diluting solvent used for determination utilizes the organic solvent used in dispersion respectively, and when the sample processed by ultrasound is measured immediately after sample adjustment, it is easy to obtain a result with less deviation and is preferred.

[0390] The photosensitive composition is preferably subjected to centrifugal separation, filtration using a sintered filter or a membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, and mixed dust. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0391] <Color filter>

[0392] The color filter of the present invention comprises a substrate and a film formed by the photosensitive composition of the present invention. The film can be used as various optical filters by appropriately selecting the type of pigment (A) used. For example, an organic pigment can be used to form a red filter segment, a green filter segment, and a blue filter segment for color filter use. Alternatively, a magenta filter segment, a cyan filter segment, and a yellow filter segment can be formed. In addition, a near-infrared absorbing pigment can be used to form a near-infrared transmission filter or a near-infrared cutoff filter.

[0393] Examples of the substrate include transparent substrates and reflective substrates. Examples of the transparent substrate include glass substrates. Examples of the reflective substrate include substrates using aluminum electrodes or metal thin films as reflective surfaces. The thickness of the substrate is preferably 0.3 μm to 4 μm.

[0394] [Method for manufacturing color filter]

[0395] The method for manufacturing the color filter is not limited, but photolithography is preferred. For example, the color filter can be manufactured by applying a photosensitive composition on a substrate to form a film (1), exposing the film in a pattern through a mask (2), developing the unexposed portion with alkali to form a patterned cured film (3), and performing a heat treatment (post-baking) on ​​the pattern (4).

[0396] Hereinafter, a method for manufacturing a color filter will be described in detail.

[0397] (Process (1))

[0398] In the step (1) of forming a film, the photosensitive composition is applied onto the substrate by a method such as spin coating, roll coating, slit coating, cast coating, or inkjet coating, and dried (pre-baked) at a temperature of about 50° C. to 120° C. for about 10 seconds to 120 seconds using an oven, a hot plate, or the like as needed.

[0399] Examples of the substrate include a glass substrate and a silicon substrate. For example, a silicon substrate may have a charge coupled device (CCD) and a complementary metal oxide semiconductor (CMOS) formed on its surface. In addition, a base coating may be provided on the substrate as needed to improve the adhesion with the upper layer, prevent the diffusion of substances, and achieve flattening of the substrate surface.

[0400] The film thickness of the coating is preferably 0.05 μm to 10.0 μm, more preferably 0.3 μm to 5 μm, as a dry film thickness.

[0401] (Process (2))

[0402] In the exposure step, for example, an exposure device such as a stepper is used to expose a specific pattern to the film obtained in step (1) through a mask. Thus, a cured film is obtained. Examples of radiation used in the exposure include ultraviolet rays such as KrF rays, g rays, h rays, and i rays.

[0403] (Process (3))

[0404] By performing an alkali development treatment on the cured film obtained in the step (2), the film in the unexposed portion is dissolved into the alkali aqueous solution, and only the cured portion remains, thereby obtaining a patterned cured film.

[0405] Examples of the developer include basic 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, and 1,8-diazabicyclo-[5.4.0]-7-undecene.

[0406] The concentration of the developer is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 1% by mass.

[0407] The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughening and peeling of the pattern are suppressed, and the residual film rate after development is increased.

[0408] Examples of the developing method include an immersion method, a spray method, and a puddle method. The developing temperature is preferably 15° C. to 40° C. After the alkali development, it is preferred to perform washing with pure water.

[0409] (Process (4))

[0410] The heat treatment (post-baking) is to heat the patterned cured film obtained in step (3) to fully harden it. The heating temperature of the post-baking is preferably 80°C to 180°C, more preferably 80°C to 120°C, and further preferably 80°C to 100°C. In addition, the heating time is preferably about 2 minutes to 1 hour, and more preferably about 3 minutes to 30 minutes.

[0411] <Image display device>

[0412] The image display device of the present invention includes a color filter.

[0413] 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.

[0414] Figure 1 The image display device 10 shown includes a pair of transparent substrates 11 and 21 which are arranged to be separated and opposed to each other, and liquid crystal LC is sealed between them.

[0415] A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0416] On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0417] A transparent protective film (not shown) is formed as needed to cover the color filter 22 , and 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 .

[0418] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Furthermore, below the polarizing plate 15, a backlight unit 30 is provided.

[0419] <Solid-state imaging device>

[0420] The solid-state imaging element of the present invention includes a color filter.

[0421] The method of the solid-state imaging element is not particularly limited, and for example, the following structure is provided: a plurality of photodiodes constituting the light receiving area of ​​the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transmission electrode including polysilicon, etc. are provided on the substrate, a light shielding film having an opening only for the light receiving portion of the photodiode is provided on the photodiode and the transmission electrode, a device protection film including silicon nitride, etc. formed in a manner covering the entire surface of the light shielding film and the light receiving portion of the photodiode is provided on the light shielding film, and a color filter is provided on the device protection film. Furthermore, it may also be a structure having a focusing component (for example, a microlens, etc., the same below) on the device protection film and below the color filter (on the side close to the substrate), or a structure having a focusing component on the color filter. In addition, the color filter may also have a structure in which a hardened film forming each color pixel is buried in a space divided into, for example, a grid shape by a partition wall. In this case, the partition wall is preferably a low refractive index relative to each color pixel.

[0422] Examples of imaging devices including the solid-state imaging element of the present invention include digital cameras and electronic devices having an imaging function (such as mobile phones and smartphones), as well as vehicle-mounted cameras and surveillance cameras.

[0423] [Example of embodiment]

[0424] Examples of embodiments of the present invention are given below. The present invention is not limited to the following.

[0425] <1> The photosensitive composition for color filter of the present specification comprises a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an acidic resin dispersant (S).

[0426] The polymerization initiator (D) contains one or more of a peroxytriazine (D1a) represented by the following general formula (1a) and a peroxytriazine (D1b) represented by the following general formula (1b).

[0427] General formula (1a)

[0428] [Chemistry 1]

[0429]

[0430] In the general formula (1a), R 1 and R 3 R independently represents a methyl group or an ethyl group. 2 It 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 a group containing an aromatic ring, and n represents an integer of 0 to 2.

[0431] General formula (1b)

[0432] [Chemistry 2]

[0433]

[0434] 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 It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, -CO-R, -YR, or -N-RR', wherein Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, 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 a group containing an aromatic ring.

[0435] <2> The photosensitive composition for color filter according to <1>, further comprising a thermosetting compound (E).

[0436] <3> The photosensitive composition for color filter according to <1> or <2>, wherein the polymerization initiator (D) further contains an oxime ester initiator (D2).

[0437] <4> A color filter including a substrate and a coating formed from the photosensitive composition for a color filter according to any one of <1> to <3>.

[0438] <5> An image display device comprising the color filter according to <4>.

[0439] <6> A solid-state imaging element comprising the color filter according to <4>.

[0440] [Example]

[0441] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In addition, "parts" means "parts by mass" and "%" means "% by mass".

[0442] Prior to the examples, each measurement method will be described.

[0443] 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.

[0444] (Average molecular weight of alkali-soluble resin and dispersion resin)

[0445] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alkali-soluble resin and the dispersed resin are measured using a gel permeation chromatograph (GPC) equipped with a refractive index (RI) detector. HLC-8220GPC (manufactured by Tosoh) was used as an apparatus, and two separation columns were connected in series. Two "TSK-GEL SUPERHZM-N" were connected and used in the fillers of the two. The measurement was performed at an oven temperature of 40°C, using a tetrahydrofuran (THF) solution as an eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent containing 1% by mass of the eluent, and 20 microliters were injected. The molecular weight is a polystyrene conversion value.

[0446] (Acid value of alkali-soluble resin and dispersion resin)

[0447] 80 ml of acetone and 10 ml of water were added to 0.5 g to 1 g of the alkali-soluble resin and the dispersed resin solution and stirred to make it uniformly dissolved, and a 0.1 mol / L KOH aqueous solution was used as a titrant and titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g). In addition, the acid value per unit non-volatile component of the resin was calculated based on the acid value of the resin solution and the non-volatile component concentration of the resin solution.

[0448] (Amine value of dispersion resin)

[0449] The amine value of the dispersion resin is a value obtained by converting the total amine value (mgKOH / g) measured according to the method of American Society for Testing Material (ASTM) D2074 into non-volatile components.

[0450] <Manufacturing of pigment (A)>

[0451] (Production of Micronized Pigment A-1)

[0452] 500 parts of anthraquinone red pigment CI Pigment Red 177 ("Cinilexred SR3C" manufactured by Cinic), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue, Ltd.) and kneaded at 120° C. for 8 hours. Next, the kneaded product was added to 5 liters of warm water and stirred for 1 hour while heating to 70° C. to prepare a slurry, and after filtering and washing with water to remove sodium chloride and diethylene glycol, the product was dried at 80° C. for a whole day and night to obtain a micronized pigment (A-1).

[0453] (Production of Micronized Pigment A-2)

[0454] 500 parts of diketopyrrolopyrrole red pigment CI Pigment Red 254 ("Irgajin Red L3630" manufactured by BASF Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 120° C. for 8 hours. Next, the kneaded product was added to 5 liters of warm water and stirred for 1 hour while heating to 70° C. to prepare a slurry, and after repeatedly filtering 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 a micronized pigment (A-2).

[0455] (Production of Micronized Pigment A-3)

[0456] 500 parts of diketopyrrolopyrrole red pigment CI Pigment Red 264 ("Cinilex red SR6T" manufactured by Cinic), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120° C. for 8 hours. Next, the kneaded product was added to 5 liters of warm water and stirred for 1 hour while heating to 70° C. to prepare a slurry, and after repeatedly filtering 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 a micronized pigment (A-3).

[0457] (Production of Micronized Pigment A-4)

[0458] 100 parts of quinophthalone yellow pigment CI Pigment Yellow 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Japan), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80° C. for 6 hours. The mixture was added to 2000 parts of warm water and stirred for 1 hour while heating to 80° C. to form a slurry, and after repeatedly filtering 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).

[0459] (Production of Micronized Pigment A-5)

[0460] 100 parts of an isoindoline yellow pigment CI Pigment Yellow 139 ("Paliotol Yellow D1819" manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader and kneaded at 60°C for 10 hours. Next, the mixture was added to 3 liters of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 80°C to form a slurry, and after repeatedly filtering and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for a day and a night to obtain a micronized pigment (A-5).

[0461] (Production of Micronized Pigment A-6)

[0462] 120 parts of CI Pigment Green 36 ("Lionol Green 6YK" manufactured by TOYOCOLOR), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 12 hours. The mixture was added to 5000 parts of warm water and stirred for 1 hour while heating to about 70°C to form a slurry, and after repeatedly filtering 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).

[0463] (Production of Micronized Pigment A-7)

[0464] 100 parts of CI Pigment Green 58 (FASTOGEN Green A110 manufactured by DIC Corporation), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70° C. for 6 hours. The kneaded product was added to 3000 parts of warm water, and stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, and after filtering and washing with water to remove sodium chloride and diethylene glycol repeatedly, it was dried at 80° C. for a whole day and night and pulverized to obtain a micronized pigment (A-7).

[0465] (Production of Micronized Pigment A-8)

[0466] 100 parts of CI Pigment Green 63, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture was poured into warm water and stirred for 1 hour with a high-speed mixer while heating to about 80° C. to form a slurry, filtered, 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).

[0467] (Production of Micronized Pigment A-9)

[0468] 100 parts of CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by TOYOCOLOR), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. The mixture was added to 3,000 parts of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 70°C to form a slurry, and after repeatedly filtering 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).

[0469] (Production of Micronized Pigment A-10)

[0470] 100 parts of CI Pigment Blue 15:3 ("Lionol Blue FG7351" manufactured by TOYOCOLOR), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. The mixture was added to 3,000 parts of warm water, and stirred for about 1 hour with a high-speed mixer while heating to about 70°C to form a slurry. After repeated filtration and water washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours and pulverized to obtain a micronized pigment (A-10).

[0471] (Production of Micronized Pigment A-11)

[0472] 100 parts of CI Pigment Violet 23 ("Lionogen Violet FG6140" manufactured by TOYOCOLOR), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. The mixture was added to 3,000 parts of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 70°C to form a slurry, and after repeatedly filtering 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-11).

[0473] <Production of near infrared absorbing pigment (a)>

[0474] The following near infrared absorbing dye (a) was prepared according to the example of Japanese Patent Application Laid-Open No. 2011-132361.

[0475] (Near infrared absorbing pigment (a))

[0476] [Chemistry 35]

[0477]

[0478] (Production of Micronized Pigment A-12)

[0479] 100 parts of infrared absorbing pigment (a), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70° C. for 6 hours. The kneaded product was added to 3000 parts of warm water, and stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, and after filtering and washing with water to remove sodium chloride and diethylene glycol, the product was dried at 80° C. for a whole day and night and pulverized to obtain a micronized pigment (A-12).

[0480] (Production of Micronized Pigment A-13)

[0481] 500 parts of diketopyrrolopyrrole red pigment CI Pigment Red 269 ("Toner Magenta F8B" manufactured by Clariant), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue, Ltd.) and kneaded at 120° C. for 8 hours. Next, the kneaded product was added to 5 liters of warm water and stirred for 1 hour while heating to 70° C. to prepare a slurry, and after repeatedly filtering 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 a micronized pigment (A-13).

[0482] (Production of Micronized Pigment A-14)

[0483] 500 parts of perylene red pigment CI Pigment Red 179 (Hostaperm Red P2GL manufactured by Hoechst), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120° C. for 8 hours. Next, the kneaded product was added to 5 liters of warm water and stirred for 1 hour while heating to 70° C. to prepare a slurry, and after filtering and washing with water to remove sodium chloride and diethylene glycol repeatedly, it was dried at 80° C. for a whole day and night to obtain a micronized pigment (A-14).

[0484] (Production of Micronized Pigment A-15)

[0485] 100 parts of quinacridone violet pigment CI Pigment Violet 19 ("CATULIA RED YP" manufactured by TOYOCOLOR), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. The mixture was added to 3,000 parts of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 70°C to form a slurry, and after repeatedly filtering 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-15).

[0486] (Production of Micronized Pigment A-16)

[0487] 100 parts of an isoindoline yellow pigment CI Pigment Yellow 185 ("Paliogen yellow D1155" manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader and kneaded at 60°C for 10 hours. Next, the mixture was added to 3 liters of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 80°C to form a slurry, and after repeatedly filtering and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for a whole day and night to obtain a micronized pigment (A-16).

[0488] (Production of Micronized Pigment A-17)

[0489] 100 parts of an isoindoline yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by Lanxess), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader and kneaded at 60°C for 10 hours. Next, the mixture was added to 3 liters of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 80°C to form a slurry, and after filtering and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for a whole day and night to obtain a micronized pigment (A-17).

[0490] <Production of alkali-soluble resin (B)>

[0491] (Alkali-soluble resin (B-1) solution)

[0492] 333 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was replaced from air to nitrogen. After the temperature was raised to 100° C., a solution prepared by adding 5.0 parts of azobisisobutyronitrile to a mixture containing 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 monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 164 parts of PGMAc was dropped into the flask from the dropping funnel over 2 hours to perform polymerization. The reaction was further continued at 100° C. for 5 hours. Next, the atmosphere in the flask was replaced from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol, (100 mol% relative to the glycidyl group of glycidyl methacrylate used in this reaction)], 0.9 parts of tris-dimethylaminomethylphenol and 0.145 parts of hydroquinone were added to the flask, and the reaction was continued at 110°C for 6 hours. The reaction was terminated when the acid value of the non-volatile component reached 1 mgKOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours to obtain a resin solution with an acid value of 80 mgKOH / g. After cooling to room temperature, about 2 parts of the resin solution were sampled, and the non-volatile component was measured by heating and drying at 180°C for 20 minutes. Subsequently, PGMAc was added in such a way that the non-volatile component became 40% by mass, thereby preparing a photosensitive alkali-soluble resin (B-1) solution. In addition, the weight average molecular weight (Mw) was 9,000.

[0493] (Alkali-soluble resin (B-2) solution)

[0494] 333 parts of PGMAc were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. After the temperature was raised to 100° C., a solution prepared by adding 5.0 parts of azobisisobutyronitrile to a mixture containing 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 monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 164 parts of PGMAc was dropped into the flask from the dropping funnel over 2 hours to perform 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 of methacrylic acid [0.5 mol, (100 mol% relative to the glycidyl group of glycidyl methacrylate used in this reaction)], 0.9 parts of tris-dimethylaminomethylphenol and 0.145 parts of hydroquinone were added to the flask, and the reaction was continued at 110°C for 6 hours. The reaction was terminated when the acid value of the non-volatile component reached 1 mgKOH / g. Next, 60.9 parts (0.40 mol) of succinic anhydride and 0.8 parts of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours to obtain a resin solution with an acid value of 100 mgKOH / g. After cooling to room temperature, about 2 parts of the resin solution were sampled, and the non-volatile component was measured by heating and drying at 180°C for 20 minutes. Subsequently, PGMAc was added in such a way that the non-volatile component became 40% by mass, thereby preparing a photosensitive alkali-soluble resin (B-2) solution. The weight average molecular weight (Mw) was 8,000.

[0495] (Alkali-soluble resin (B-3) solution)

[0496] 207 parts of cyclohexanone were placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube and a stirring device in a separable four-necked flask, and the temperature was raised to 80°C. After nitrogen substitution in the reaction vessel, a mixture of 20 parts of methacrylic acid, 20 parts of p-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 0.99 parts of 2,2'-azobisisobutyronitrile was dropped from the dropping tube over 2 hours to perform polymerization. After the dropwise addition was completed, the reaction was continued for 3 hours to obtain a resin solution. Next, for the obtained resin solution, after stirring while stopping nitrogen and injecting dry air for 1 hour, it was cooled to room temperature, and then a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C for 3 hours. After the addition was completed, the reaction was continued for 1 hour to obtain a resin solution. After cooling to room temperature, about 2 parts of the resin solution were sampled, and the non-volatile components were measured by heating and drying at 180°C for 20 minutes. Subsequently, cyclohexanone was added in a manner such that the non-volatile components became 40% by mass, thereby preparing an alkali-soluble resin (B-3) solution. The weight average molecular weight (Mw) was 22,050.

[0497] (Alkali-soluble resin (B-4) solution)

[0498] 182 parts of PGMAC were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. After the temperature was raised to 100° C., a solution prepared by adding 3.0 parts of azobisisobutyronitrile to a mixture containing 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 into the flask from the dropping funnel over 2 hours to perform 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 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% relative to the carboxyl group of methacrylic acid used in this reaction)], 0.9 parts of tris-dimethylaminomethylphenol and 0.145 parts of hydroquinone were added to 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 were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile component. Subsequently, PGMAc was added in such a way that the non-volatile component became 40% by mass, thereby preparing an alkali-soluble resin (B-4) solution. The weight average molecular weight (Mw) was 14,960.

[0499] (Alkali-soluble resin (B-5) solution)

[0500] 196 parts of cyclohexanone were placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube and a stirring device in a separable four-necked flask, and the temperature was raised to 80°C. After nitrogen substitution in the reaction vessel, a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of p-cumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 2.0 parts of 2,2'-azobisisobutyronitrile was dropped from the dropping tube over 2 hours, and polymerization was performed. After the dropwise addition was completed, 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 were sampled, and the non-volatile components were measured by heating and drying at 180°C for 40 minutes. Then, PGMAc was added so that the nonvolatile content became 40% by mass to prepare an alkali-soluble resin (B-5) solution. The weight average molecular weight (Mw) was 20,000.

[0501] (Alkali-soluble resin (B-6) solution)

[0502] After 257.3 parts of PGMAc was placed in a flask including a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, the mixture was stirred while nitrogen substitution was performed and the temperature was raised to 78°C. Next, 22.4 parts of dicyclopentyl 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-diethylmalonate manufactured by Showa Denko K.K.), and 11.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were added and dissolved in 78.7 parts of PGMAc, and the mixture was added dropwise from the dropping funnel to the flask. After completion of the dropping, the mixture was reacted at 78°C for 3 hours. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass to prepare an alkali-soluble resin (B-6) solution. The alkali-soluble resin (B-6) had an acid value of 111 mgKOH / g and a weight average molecular weight of 9,500.

[0503] <Synthesis of triazine peroxide>

[0504] [Synthesis Example 1: Synthesis of Peroxytriazine Compound 1a (D1a-1 / Compound 1)]

[0505] 1.66 parts of ion exchange water and 0.553 parts (6.64 mmol) of 48% sodium hydroxide aqueous solution were added to a 20 mL eggplant flask, and 0.698 parts (5.31 mmol) of 69% tert-butyl hydroperoxide aqueous solution were slowly added at 30°C or below. A mixed solution of 0.500 parts (2.21 mmol) of 2,4-dichloro-6-phenyl-1,3,5-triazine and 1 mL of tetrahydrofuran was added dropwise at 10°C for 10 minutes, and the mixture was reacted at 20°C for 3.5 hours. After the reaction was completed, 10 mL of dichloromethane was added and the aqueous phase was separated. The oil phase was washed with ion exchange water and dried with anhydrous magnesium sulfate at 0°C. After filtration, the oil phase was concentrated under reduced pressure to obtain 0.683 parts (yield 92%) of the peroxytriazine compound 1a (D1a-1 / compound 1) of the present invention.

[0506] [Synthesis Example 2: Synthesis of Peroxytriazine Compound 2a (D1a-2 / Compound 32)]

[0507] 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 in a 300 mL eggplant flask and stirred under ice bath. After 15 minutes, 4.43 parts (33.2 mmol) of aluminum chloride were added and the temperature was raised to room temperature. After 1 hour, the reaction solution was injected into 75 mL of 1M hydrochloric acid cooled in an ice bath, and the aqueous phase was separated. The oil 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 crude yellow solid. The crude body was purified by silica gel column chromatography (n-hexane / toluene = 4 / 1 to 1.5 / 1) to obtain 8.05 parts (yield 83%) of 2,4-dichloro-6-(4-methoxy-1-naphthyl)-1,3,5-triazine.

[0508] 0.815 parts of ion exchange water and 0.272 parts (3.26 mmol) of 48% sodium hydroxide aqueous solution were added to a 30 mL eggplant flask, and 0.276 parts (2.61 mmol) of 69% tert-amyl hydroperoxide were slowly added at 30°C or below. A mixed solution of 0.300 parts (1.09 mmol) of 2,4-dichloro-6-(1-naphthyl)-1,3,5-triazine and 3 mL of tetrahydrofuran was added dropwise at 10°C for 10 minutes, and the mixture was reacted at 20°C for 2 hours. After the reaction was completed, the reaction solution was added to 50 mL of ice water. The precipitated crystals were filtered, washed with ion exchange water, and dried under reduced pressure to obtain the peroxytriazine compound 2a (D1a-2 / compound 32) of the present invention.

[0509] [Synthesis Example 3: Synthesis of Peroxytriazine Compound 3a (D1a-3 / Compound 37)]

[0510] Into a 500mL three-necked flask dried by heating, 1.69 parts (69.5mmol) of magnesium, 57mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were placed and stirred at room temperature. After adding a mixed solution of 13.34 parts (50.7mmol) of 4-bromo-4'-methoxybiphenyl and 57mL of dehydrated tetrahydrofuran, reflux stirring was performed. After 1 hour, the internal temperature was cooled to below -60°C. It took 15 minutes to drop a mixed solution of 8.92 parts (48.4mmol) of cyanuric chloride and dehydrated tetrahydrofuran prepared separately. After that, it took 30 minutes to warm to room temperature and stirred in a water bath. After 62 hours, the reaction solution was cooled in an ice bath, 1M hydrochloric acid was added, and the pH was adjusted to 8 with a saturated sodium bicarbonate aqueous solution. Then, 160mL of ion exchange water was added and extracted with ethyl acetate. After washing the oil phase once with saturated brine, it was dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 14.6 parts of a crude product, which 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-naphthyl)-1,3,5-triazine.

[0511] 0.815 parts of ion exchange water and 0.272 parts (3.26 mmol) of 48% sodium hydroxide aqueous solution were added to a 30 mL eggplant flask, and 0.276 parts (2.61 mmol) of 85% tert-amyl hydroperoxide were slowly added at 30°C or below. A mixed solution of 0.300 parts (1.09 mmol) of 2,4-dichloro-6-(1-naphthyl)-1,3,5-triazine and 3 mL of tetrahydrofuran was added dropwise at 10°C for 10 minutes, and the mixture was reacted at 20°C for 2 hours. After the reaction was completed, the reaction solution was added to 50 mL of ice water. The precipitated crystals were filtered, washed with ion exchange water, and dried under reduced pressure to obtain 0.216 parts (yield 52%) of peroxy triazine compound 3a (D1a-3 / compound 37).

[0512] [Synthesis Example 4: Synthesis of Peroxytriazine Compound 4a (D1a-4 / Compound 46)]

[0513] A peroxytriazine 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.

[0514] [Synthesis Example 5: Synthesis of Peroxytriazine Compound 1b (D1b-1 / Compound 19b)]

[0515] 3.03 parts (16.3 mmol) of diphenyl sulfide and 30 mL of dehydrated dichloromethane were added to a 100 mL eggplant flask and cooled to 0°C. After adding 3.00 parts (16.3 mmol) of cyanuric chloride, 2.39 parts (17.9 mmol) of aluminum chloride were added over 10 minutes, and the mixture was reacted at 0°C for 3 hours. After the reaction was completed, the reaction solution was injected into 50 mL of 1M hydrochloric acid cooled in an ice bath and stirred, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, the crude body was concentrated under reduced pressure. The crude body 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.

[0516] 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 to a 100 mL eggplant flask and heated to 40°C. After adding 4.67 parts of ion exchange water and 4.31 parts (26.9 mmol) of a 25% by mass sodium hydroxide aqueous solution, 0.32 parts (9.87 mmol) of methanol was added dropwise over 10 minutes, and the mixture was reacted at 40°C for 2 hours. 1.29 parts (9.87 mmol) of a 69% by mass tert-butyl hydroperoxide aqueous solution was added dropwise at 40°C or below over 10 minutes, and the mixture was reacted at 40°C for 1 hour. After the reaction was completed, the aqueous phase was separated, and the oil phase was added to 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 peroxytriazine compound 1b (D1b-1 / Compound 19b) of the present invention.

[0517] [Synthesis Example 6: Synthesis of Peroxytriazine Compound 2b (D1b-2 / Compound 25b)]

[0518] A peroxytriazine compound 2b (D1b-2 / Compound 25b) was obtained by performing synthesis in the same manner as in Synthesis Example 1 except that the diphenyl sulfide used in Synthesis Example 1 was changed to 1-methoxynaphthalene.

[0519] [Synthesis Example 7: Synthesis of Peroxytriazine Compound 3b (D1b-3 / Compound 35b)]

[0520] In a 100mL three-necked flask dried by heating, 0.44 parts (17.1mmol) of magnesium, 15mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were placed and stirred at room temperature. After adding a mixed solution of 4.29 parts (16.3mmol) of 4-bromo-4'-methoxybiphenyl and 15mL of dehydrated tetrahydrofuran, reflux stirring was performed for 1 hour. 3.00 parts (16.3mmol) of cyanuric chloride and 15mL of dehydrated tetrahydrofuran were added to another 100mL three-necked flask and cooled to 0°C. It took 30 minutes to drop the previously prepared mixed solution therein, warm to room temperature and stir for 15 hours. The reaction solution was cooled with an ice bath, 1M hydrochloric acid was added and stirred, and the pH was adjusted to 8 with a saturated sodium bicarbonate aqueous solution. Then, extraction was performed with ethyl acetate. After washing the oil phase once with saturated saline, dehydration was performed with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude body. 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.

[0521] 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 to a 50 mL eggplant flask and heated to 40°C. After adding 1.88 parts of ion exchange water and 1.74 parts (10.9 mmol) of a 25% by mass sodium hydroxide aqueous solution, 0.13 parts (3.98 mmol) of methanol was added dropwise over 5 minutes, and the mixture was reacted at 40°C for 2 hours. 0.52 parts (3.98 mmol) of a 69% by mass tert-butyl hydroperoxide aqueous solution was added dropwise at 40°C or below over 5 minutes, and the mixture was reacted at 40°C for 1 hour. After the reaction was completed, the aqueous phase was separated, and the oil phase was added to 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 peroxytriazine compound 3b (D1b-3 / Compound 35b) of the present invention.

[0522] [Synthesis Example 8: Synthesis of Peroxytriazine Compound 4b (D1b-4 / Compound 48b)]

[0523] Peroxytriazine compound 4b (D1b-4 / Compound 48b) was synthesized in the same manner as in Synthesis Example 7 except that methanol used in Synthesis Example 7 was changed to ethanol and the 69 mass % tert-butyl hydroperoxide aqueous solution was changed to 85 mass % tert-amyl hydroperoxide solution.

[0524] [Synthesis Example 9: Synthesis of Peroxytriazine Compound 5b (D1b-5 / Compound 53b)]

[0525] Peroxytriazine compound 5b (D1b-5 / Compound 53b) was synthesized in the same manner as in Synthesis Example 7 except that methanol used in Synthesis Example 7 was changed to isopropyl alcohol and the 69 mass % tert-butyl hydroperoxide aqueous solution was changed to a 90 mass % tert-hexyl hydroperoxide solution.

[0526] [Synthesis Example 10: Synthesis of Peroxytriazine Compound 6b (D1b-6 / Compound 56b)]

[0527] Peroxytriazine compound 6b (D1b-6 / Compound 56b) was synthesized in the same manner as in Synthesis Example 7 except that methanol used in Synthesis Example 7 was changed to tert-butyl alcohol and the 69 mass % tert-butyl hydroperoxide aqueous solution was changed to 80 mass % cumene hydroperoxide solution.

[0528] [Synthesis Example 11: Synthesis of Peroxytriazine Compound 7b (D1b-7 / Compound 77b)]

[0529] In a 100mL three-necked flask dried by heating, 0.44 parts (17.1mmol) of magnesium, 15mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were placed and stirred at room temperature. After adding a mixed solution of 4.29 parts (16.3mmol) of 4-bromo-4'-methoxybiphenyl and 15mL of dehydrated tetrahydrofuran, reflux stirring was performed for 1 hour. In another 100mL three-necked flask, 3.00 parts (16.3mmol) of cyanuric chloride and 15mL of dehydrated tetrahydrofuran were added and cooled to 0°C. It took 30 minutes to drop the previously prepared mixed solution therein, raise the solution temperature to 25°C, and stir for 15 hours to react. After the reaction was completed, the solution was cooled in an ice bath, 1M hydrochloric acid was added and stirred, and the pH was adjusted to 8 using a saturated sodium bicarbonate aqueous solution. Then, extraction was performed using ethyl acetate. After the oil phase was washed once with saturated brine, it was dehydrated using magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude product, which 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.

[0530] Add 3.03 parts (16.3 mmol) of anisole and 30 mL of dehydrated dichloromethane to a 100 mL eggplant flask and cool to 0°C. Add 3.00 parts (16.3 mmol) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine, add 2.39 parts (17.9 mmol) of aluminum chloride over 10 minutes, and react at 0°C for 3 hours. After the reaction is completed, inject the reaction solution into 50 mL of 1M hydrochloric acid cooled in an ice bath and stir to separate the aqueous phase. Wash the oil phase with 50 mL of saturated brine and dehydrate with anhydrous sodium sulfate. After filtration, concentrate 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-chloro-4-(4-methoxyphenyl)-6-[4-(4′-methoxybiphenyl)]-1,3,5-triazine.

[0531] 1.88 parts of ion exchange water and 1.74 parts (10.9 mmol) of 25% sodium hydroxide aqueous solution were added to a 50 mL eggplant flask, and 0.52 parts (3.98 mmol) of 69% tert-butyl hydroperoxide aqueous solution were slowly added at 30°C or below. 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 for 10 minutes, and the mixture was reacted at 20°C for 3 hours. After the reaction was completed, 10 mL of dichloromethane was added to separate the aqueous phase. The oil phase was washed with ion exchange water and dried with anhydrous magnesium sulfate at 0°C. After filtration, the oil phase was concentrated under reduced pressure to obtain 1.04 parts (yield 75.0%) of the peroxytriazine compound 7b (D1b-7 / compound 77b) of the present invention.

[0532] [Synthesis Example 12: Synthesis of Peroxytriazine Compound 8b (D1b-8 / Compound 81b)]

[0533] 3.00 parts (16.3 mmol), 30 mL of dehydrated dichloromethane, and 4.35 parts (32.6 mmol) of aluminum chloride were added to a 100 mL eggplant flask and cooled to 20°C. 5.16 parts (32.6 mmol) of 1-methoxynaphthalene were added thereto over 15 minutes, and the mixture was reacted at 20°C for 3 hours. After the reaction, the reaction solution was cooled to 0°C, 50 mL of 1M hydrochloric acid was added and stirred in an ice bath, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, the mixture was concentrated under reduced pressure to obtain 5.48 parts (yield 78.6%) of 2-chloro-4,6-bis(4-methoxy-1-naphthyl)-1,3,5-triazine in crude form.

[0534] 3.00 parts (5.45 mmol) of crude 2-chloro-4,6-bis(4-methoxy-1-naphthyl)-1,3,5-triazine and 30 mL of tetrahydrofuran were added to a 100 mL eggplant flask and heated to 40°C. A mixed solution of 2.18 parts (10.9 mmol) of a 20% by mass sodium hydroxide aqueous solution and 1.42 parts (10.9 mmol) of a 69% by mass tert-butyl hydroperoxide aqueous solution was added dropwise thereto over 10 minutes, and the mixture was reacted at 40°C for 4 hours. After the reaction was completed, 50 mL of dichloromethane was added to separate the aqueous phase. The oil phase was washed with ion exchange water and dried with anhydrous magnesium sulfate at 0°C. After filtration, the crude product was obtained by concentration under reduced pressure. The crude product was purified by silica gel column chromatography (using dichloromethane) to obtain 1.63 parts (yield 62.3%) of the peroxytriazine compound 8b (D1b-8 / Compound 81b) of the present invention.

[0535] <Production of acidic resin dispersant (S)>

[0536] (Acidic resin dispersant (S-1) solution)

[0537] In a 500mL round-bottom four-mouth separable flask including a cooling tube, a dropping funnel, a nitrogen introduction tube, a stirrer, and a thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethyl ketone methyl trimethyl silyl acetal as an initiator were added via a dropping funnel, and nitrogen substitution was fully performed. A syringe was used to inject 0.5 parts by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium meta-chlorobenzoate as a catalyst, and a dropping funnel was used to drop 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 for 60 minutes. The reaction flask was cooled by an ice bath and the temperature was maintained at less than 40°C. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide was added dropwise for 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, filtered and vacuum dried for purification. Then, 15.0 parts by mass of the obtained block copolymer was 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 relative to dimethylaminopropyl methacrylamide) as a salt-forming component was added, stirred at a reaction temperature of 30° C. for 20 hours, and PGMAC was added for adjustment to obtain an acidic resin-type dispersant (S-1) solution having a non-volatile component of 40%.

[0538] (Acidic resin dispersant (S-2) solution)

[0539] Into a reaction vessel including a nitrogen inlet tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged, and replaced with nitrogen. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of PGMAc was reacted for 7 hours. It was confirmed by measuring the non-volatile component that 95% of the reaction was carried out. Subsequently, 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 allowed to proceed at 100°C for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to dilute the mixture so that the non-volatile content was 40%, thereby obtaining a comb-shaped acidic resin dispersant (S-2) solution having an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500.

[0540] <Manufacturing of dispersion>

[0541] (Dispersion 1)

[0542] The following raw materials were stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eiger mill ("Mini Model M-250MKII" manufactured by Eiger Japan), and then filtered using a filter with a pore size of 1.0 μm to prepare a dispersion 1 having a non-volatile content of 20%. The organic solvent (O-1) was PGMAc.

[0543] Micronized pigment (A-1): 12.00 parts

[0544] Acidic resin dispersant (S-1) solution: 10.00 parts

[0545] Acidic resin dispersant (S-2) solution: 10.00 parts

[0546] Organic solvent (Q-1): 68.00 parts

[0547] Dispersions 1 to 18 were obtained in the same manner as in Dispersion 1 except that the materials and blending amounts of Dispersion 1 were changed as described in Table 1-1 and Table 1-2.

[0548] [Table 1-1]

[0549]

[0550] [Table 1-2]

[0551]

[0552] Details of the abbreviations in Table 1 are as follows.

[0553] Pigment derivatives (N-1)

[0554] [Chemistry 36]

[0555]

[0556] Pigment derivatives (N-2)

[0557] [Chemistry 37]

[0558]

[0559] Pigment derivatives (N-3)

[0560] [Chemistry 38]

[0561]

[0562] Pigment derivative (N-4)

[0563] [Chemistry 39]

[0564]

[0565] Pigment derivative (N-5)

[0566] [Chemistry 40]

[0567]

[0568] Micronized pigment (A-18): Carbon black ("#850" manufactured by Mitsubishi Chemical Corporation)

[0569] <Production of photosensitive composition>

[0570] [Example 1]

[0571] (Photosensitive composition 1)

[0572] The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive composition 1 having a nonvolatile content of 15%.

[0573] Dispersion 4: 11.25 parts

[0574] Dispersion 5: 3.75 parts

[0575] Dispersion 6: 22.50 parts

[0576] Alkali soluble resin (B-1) solution: 7.88 parts

[0577] Polymerizable compound (C-2): 3.00 parts

[0578] Polymerization initiator (Da-1): 0.30 parts

[0579] Polymerization initiator (D2-1): 0.15 parts

[0580] Thermosetting compound (E-1): 0.75 parts

[0581] Ultraviolet absorber (F-1): 0.15 parts

[0582] Leveling agent (L): 1.00 part

[0583] Organic solvent (O): 49.28 parts

[0584] [Polymerizable compound (C)]

[0585] C-1: NK ester A-DCP (tricyclodecane dimethanol diacrylate difunctional acrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0586] C-2: Aronix M-306 (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, trifunctional to tetrafunctional acrylate: manufactured by Toa Gosei Co., Ltd.)

[0587] C-3: Aronix M-402 (dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate pentafunctional to hexafunctional acrylate: manufactured by Toa Gosei Co., Ltd.)

[0588] ·C-4: UA-306H (hexafunctional urethane acrylate: manufactured by Kyoeisha Chemical Co., Ltd.)

[0589] C-5: Aronix M-520 (polyacid-modified acrylic oligomer pentafunctional acrylate: manufactured by Toa Gosei Co., Ltd.)

[0590] [Polymerization initiator (D)]

[0591] D1a-1: Compound 1 of triazine peroxide (D1a)

[0592] D1a-2: Compound 32 of triazine peroxide (D1a)

[0593] D1a-3: Compound 37 of triazine peroxide (D1a)

[0594] D1a-4: Compound 46 of triazine peroxide (D1a)

[0595] D1b-1: Compound 19b of triazine peroxide (D1b)

[0596] D1b-2: Compound 25b of triazine peroxide (D1b)

[0597] D1b-3: Compound 35b of triazine peroxide (D1b)

[0598] D1b-4: Compound 48b of triazine peroxide (D1b)

[0599] D1b-5: Compound 53b of triazine peroxide (D1b)

[0600] D1b-6: Compound 56b of triazine peroxide (D1b)

[0601] D1b-7: Compound 77b of triazine peroxide (D1b)

[0602] D1b-8: Compound 81b of triazine peroxide (D1b)

[0603] D2-1: ADEKA ARKLS NCI-831 (manufactured by ADEKA Corporation; oxime-based photopolymerization initiator (D21) represented by the chemical formula (D21-2), with an absorption coefficient of 13,410 L / mol·cm for light with a wavelength of 365 nm)

[0604] D2-2: PBG-345 (manufactured by Changzhou Qiangli Company; oxime-based photopolymerization initiator (D22) represented by chemical formula (D22-1), with an absorption coefficient of 18,334 L / mol·cm for light with a wavelength of 365 nm)

[0605] D2-3: Irgacure OXE-04 (manufactured by BASF Japan; oxime-based photopolymerization initiator (D23) represented by chemical formula (D23-1), with an absorption coefficient of 7,051 L / mol·cm for light with a wavelength of 365 nm)

[0606] D2-4: Irgacure OXE-01 (manufactured by BASF Japan; oxime-based photopolymerization initiator (D24) represented by chemical formula (D24-1), with an absorption coefficient of 3,884 L / mol·cm for light with a wavelength of 365 nm)

[0607] D2-5: ADEKA ARKLS NCI-730 (manufactured by ADEKA Corporation; oxime-based photopolymerization initiator (D25) represented by the chemical formula (D25-6), with an absorption coefficient of 8,423 L / mol·cm for light with a wavelength of 365 nm)

[0608] D3-1: Irgacure 907 (α-amino alkyl phenoxide; manufactured by BASF Japan)

[0609] D3-2: Irgacure 369 (α-amino alkyl phenoxide; manufactured by BASF Japan)

[0610] D3-3: NPI-20400 (α-aminophenyl alkyl ketone; manufactured by Changzhou Qiangli Company)

[0611] [Thermosetting compound (E)]

[0612] E-1: EHPE-3150 (epoxy compound; manufactured by Daicel Chemical Co., Ltd.)

[0613] E-2: DENACOL EX-611 (epoxy compound; manufactured by Nagase Industries, Ltd.)

[0614] E-3: Duranate MF-K60B (isocyanurate of hexamethylene diisocyanate blocked with an active methylene compound; manufactured by Asahi Kasei Corporation)

[0615] E-4: Aron Oxetane OXT-121 (oxetane compound; manufactured by Toa Synthetics Co., Ltd.)

[0616] [Ultraviolet absorber (F)]

[0617] F-1: TINUVIN 326 (2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole; manufactured by BASF Japan)

[0618] [Leveling agent (L)]

[0619] One part of each of BYK-330 (manufactured by BYK-Chemie) and Megafac F-551 (manufactured by DIC Corporation) was mixed and dissolved in 98 parts of PGMAc, and the obtained mixed solution was used as a leveling agent (L).

[0620] [Organic solvent (O)]

[0621] 80 parts of propylene glycol monomethyl ether acetate, 10 parts of cyclohexanone, and 10 parts of ethyl 3-ethoxypropionate were mixed to prepare an organic solvent (O).

[0622] The same method as in Example 1 was followed except that the type and amount of the formulation were changed so that the formulation of Example 1 had the structural ratios described in Tables 2 to 8, thereby obtaining photosensitive compositions of Examples 2 to 70 and Comparative Example 1. In the following table, the content of D1 is the content of triazine peroxide (D1) in the nonvolatile component of the photosensitive composition. The mass ratio of D1 to D2 is the mass ratio of triazine peroxide (D1): oxime ester initiator (D2).

[0623] [Table 2]

[0624]

[0625] [Table 3]

[0626]

[0627] [Table 4]

[0628]

[0629] [Table 5]

[0630]

[0631] [Table 6]

[0632]

[0633] [Table 7]

[0634]

[0635] [Table 8]

[0636]

[0637] <Evaluation of photosensitive composition>

[0638] The line width, adhesion, and chemical resistance of the obtained Examples 1 to 70 and Comparative Example 1 were evaluated by the following methods. The evaluation results are shown in Table 9.

[0639] [Line width evaluation]

[0640] The obtained photosensitive composition was applied to a 100 mm × 100 mm, 0.7 mm thick glass substrate (Eagle 2000 manufactured by Corning) using a spin coater so that the dry film thickness was 3.0 μm, and dried on a hot plate at 90° C. for 2 minutes. Then, an ultra-high pressure mercury lamp was used at an illumination of 30 mW / cm 2 、100mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a 50 μm wide stripe pattern. After cooling the substrate to room temperature, the substrate was spray-developed at 23° C. for 70 seconds using an organic alkali developer, tetramethylammonium hydroxide (hereinafter referred to as TMAH), washed with ion exchange water and air-dried, and heated at 100° C. for 20 minutes in a clean oven to form a stripe pattern on the substrate. The pattern was observed using an optical microscope and the line width was evaluated.

[0641] The evaluation criteria are as follows, and 2 or more is within the practical range.

[0642] 4: Compared with the mask opening, -1μm≤line width≤1μm.

[0643] 3: Compared with the mask opening, -3μm≤line width<-1μm or 1μm<line width≤3μm.

[0644] 2: Compared with the mask opening, -5μm≤line width<-3μm or 3μm<line width≤5μm.

[0645] 1: Line width <-5μm or line width <5μm compared to the mask opening.

[0646] [Adhesion evaluation (1)]

[0647] The obtained photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm by spin coating so that the film thickness after drying was 3.0 μm, and dried on a hot plate at 90°C for 2 minutes. Then, after the substrate was cooled to room temperature, an ultra-high pressure mercury lamp was used to illuminate the photomask with a stripe pattern of 5 μm, 10 μm, 15 μm, 20 μm and 25 μm with a width of 5 μm as the scale, at an illumination of 30 mW / cm 2 、100mJ / cm 2Expose. After that, the substrate was spray-developed using TMAH at 23°C, washed with ion exchange water and air-dried, and heated in a clean oven at 100°C for 20 minutes to obtain an evaluation substrate. Spray development is performed for the film in each photosensitive composition within the shortest time in which a pattern can be formed without residual development, and this is taken as the appropriate development time. The fine line pattern with a width of 5μm to 25μm in the pattern of the evaluation substrate was observed using an optical microscope to confirm the minimum line width of the remaining fine line pattern.

[0648] The evaluation criteria are as follows, and 2 or more is within the practical range.

[0649] 4: A thin line of less than 10 μm remains.

[0650] 3: A thin line exceeding 10 μm and not more than 15 μm remains.

[0651] 2: A thin line exceeding 15 μm and not more than 20 μm remains.

[0652] 1: No fine lines of 20 μm or less remain.

[0653] [Adhesion evaluation (2)]

[0654] At an illumination of 30mW / cm 2 、60mJ / cm 2 Evaluation was performed in the same manner as in the adhesion evaluation (1), except that exposure was performed.

[0655] [Chemical resistance evaluation]

[0656] The substrate was exposed to light through a photomask having a stripe pattern of 100 μm in width, and the substrate was prepared in the same manner as the adhesion evaluation. The chromaticity ([L*(1), a*(1), b*(1)]) of the 100 μm stripe pattern of the prepared substrate under light source C was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optics Corporation). After that, it was immersed in N-methylpyrrolidone for 30 minutes, washed with ion exchange water and air-dried. Then, the chromaticity ([L*(2), a*(2), b*(2)]) of the 100 μm stripe pattern under light source C was measured, and the color difference ΔE*a*b* was calculated using the following calculation formula.

[0657] The evaluation criteria are as follows, and 2 or more is within the practical range.

[0658] ΔE*a*b*={(L*(2)-L*(1)) 2 +(b*(2)-b*(1)) 2 +(a*(2)-a*(1)) 2} 0.5

[0659] 4: ΔE*a*b* is less than 1.

[0660] 3: ΔE*a*b* is 1 or more and less than 2.

[0661] 2: ΔE*a*b* is 2 or more and less than 3.

[0662] 1: ΔE*a*b* is 3 or more.

[0663] [Table 9]

[0664]

Claims

1. A photosensitive composition for a color filter, comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an acidic resin dispersant (S), wherein: The polymerization initiator (D) contains one or more of a peroxytriazine (D1a) represented by the following general formula (1a) and a peroxytriazine (D1b) represented by the following general formula (1b). General formula (1a) In the 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 is a group containing an aromatic ring, and n represents an integer from 0 to 2, General formula (1b) 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 It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, -CO-R, -YR, or -N-RR', wherein Y represents an oxygen atom or a sulfur atom, and R and R' independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, 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; and X represents a group containing an aromatic ring. 2 . The photosensitive composition for color filter according to claim 1 , comprising a thermosetting compound (E). 3 . The photosensitive composition for color filter according to claim 1 , wherein the polymerization initiator (D) further comprises an oxime ester initiator (D2). 4 . A color filter comprising a substrate and a coating formed from the photosensitive composition for a color filter according to claim 1 .

5. An image display device comprising the color filter according to claim 4. 6 . A solid-state imaging element comprising the color filter according to claim 4 .

Images