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

Abstract

To provide a photosensitive composition which enables formation of a pattern that has excellent pattern formation property (line width, cross-sectional shape and residual film property), and is excellent in solvent resistance.SOLUTION: A photosensitive composition contains a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the coloring agent (A) contains two or more kinds of metal azo compounds which are selected from the group consisting of a metal azo compound represented by the following general formula (1) and a metal azo compound of its tautomeric structure and have at least different metal species, and a coloring agent (A1) containing a compound represented by general formula (2), and the polymerization initiator (D) contains a polymerization initiator (D1) having two oxime groups in one molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a photosensitive composition and its uses. [Background technology]

[0002] In recent years, the demand for color filters used in liquid crystal displays, organic light-emitting diodes (OLEDs), digital cameras, smartphones, and infrared sensors has been growing due to their widespread adoption. Color filters separate passing light into its constituent colors, which are then combined to form an image. Therefore, color filters are required to offer higher brightness, higher contrast, and improved color reproduction.

[0003] Patent documents 1 to 4 disclose a metal pigment containing azobarbituric acid, two or more metal ions, and a melamine compound as a pigment with improved coloring performance. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-171912 [Patent Document 2] Japanese Patent Publication No. 2017-171913 [Patent Document 3] Japanese Patent Publication No. 2017-171914 [Patent Document 4] Japanese Patent Publication No. 2017-171915 [Overview of the project] [Problems that the invention aims to solve]

[0005] Color filters are manufactured, for example, through the following process: 1. A photosensitive composition is applied to a transparent substrate such as glass, and the solvent is removed from the coating by drying. 2. The coating is irradiated and cured (hereinafter referred to as exposure) with ultraviolet light or the like through a photomask having a desired pattern shape. 3. The unexposed parts of the coating are then washed and removed with a developer (hereinafter referred to as development). 4. If necessary, the cured film is heat-treated (hereinafter referred to as post-bake) to fully harden it, thereby obtaining the first color pattern. The same procedure is then repeated to form patterns of other colors and manufacture the color filter. Therefore, the photosensitive composition used to form the color filter must have pattern-forming properties (line width, cross-sectional shape, residual film properties). Furthermore, the composition must be resistant to solvents contained in the composition used to form the alignment film and overcoat layer on top of the color filter.

[0006] After thorough investigation into metal pigments containing azobarbituric acid, two or more metal ions, and melamine compounds, it was found that photosensitive compositions containing these metal azo pigments had problems with pattern formation and solvent resistance.

[0007] On the other hand, Patent Documents 1 to 4 do not include any studies on pattern formation properties (line width, cross-sectional shape, residual film properties) or solvent resistance.

[0008] The present invention aims to provide a photosensitive composition that can form patterns with excellent pattern-forming properties (line width, cross-sectional shape, residual film) and excellent solvent resistance. [Means for solving the problem]

[0009] The present invention relates to a photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), The coloring agent (A) comprises a coloring agent (A1) containing at least two different metal azo compounds selected from the group consisting of a metal azo compound represented by the following general formula (1) and a metal azo compound having a tautomer structure thereof, and a compound represented by the following general formula (2). The photosensitive composition in which the polymerization initiator (D) contains a polymerization initiator (D1) having two oxime groups in one molecule. General formula (1)

Chemical formula

Chemical formula

Advantages of the Invention

[0010] According to the present invention described above, it is possible to provide a photosensitive composition having excellent pattern forming properties (line width, cross-sectional shape, residual film properties) and capable of forming a pattern excellent in solvent resistance. Further, the present invention can provide a color filter, a solid-state imaging device, and an image display device.

Modes for Carrying Out the Invention

[0011] Hereinafter, modes for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0012] In this invention, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; issued by The Society of Dyers and Colourists). A polymerizable unsaturated group is an ethylenically unsaturated double bond. Furthermore, regarding the molecular weight of the compounds in this invention, for low molecular weight compounds whose molecular weight can be determined, the value is calculated (formula weight) or measured by ESI-MS (electrospray ionization mass spectrometry), and for compounds with a molecular weight distribution, the weight-average molecular weight in polystyrene terms is measured by gel permeation chromatography using tetrahydrofuran as the solvent. A monomer is a compound that forms a resin through polymerization. A monomer is in an unreacted state, while a monomer unit is the state in which the monomer has polymerized and formed a resin. A polymerizable compound is a compound that forms a film through polymerization.

[0013] <Photosensitive composition> One embodiment of the present invention relates to a photosensitive composition. The photosensitive composition of the present invention comprises a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), The coloring agent (A) includes a coloring agent (A1) comprising at least two different metal azo compounds selected from the group consisting of a metal azo compound represented by the following general formula (1) and a metal azo compound having a tautomer structure thereof, and a compound represented by the following general formula (2). The polymerization initiator (D) is characterized by containing a polymerization initiator (D1) having two oxime groups in one molecule. General formula (1) [ka] (In general formula (1), R1 and R2 each independently represent OH, NH2, or NHR5; R3 and R4 each independently represent =O or =NR5; and R5 represents a hydrogen atom or an optionally substituted alkyl group. Me is a metal ion selected from the group consisting of Ni, Zn, Cu, Al, Fe, Co, and Mn.)

[0014] General formula (2) [ka] (In general formula (2), each of the three R6 atoms independently represents a hydrogen atom or an alkyl group which may have substituents.)

[0015] The mechanism by which the above-described photosensitive composition can solve the problems of the present invention is not clear, but we speculate as follows.

[0016] In contrast to the reduced pattern-forming ability and solvent resistance caused by the use of colorant (A1), polymerization initiator (D1), which has two oxime groups in its molecule, has high radical generation ability and high reactivity even in small amounts. Therefore, it is presumed that by compensating for the aforementioned drawbacks, chipping, peeling, and elution of unreacted substances during the development process will be suppressed, and a superior pattern can be formed. Furthermore, it is presumed that a film with high solvent resistance will be formed as curing proceeds sufficiently.

[0017] The components included in or potentially included in one embodiment of the photosensitive composition will be described in detail below.

[0018] [Coloring agent (A)] (Coloring agent (A1)) The photosensitive composition of the present invention includes, as a colorant (A), a colorant (A1) (hereinafter also simply referred to as colorant (A1)) containing at least two or more metal azo compounds with different metal species selected from the group consisting of a metal azo compound represented by the following general formula (1) and a metal azo compound having a tautomer structure thereof, and a compound represented by the following general formula (2). At least two or more metal azo compounds with different metal species means including two or more metal azo compounds with different types of metal ions relative to each other.

[0019] General formula (1) [ka]

[0020] In general formula (1), R1 and R2 each independently represent OH, NH2, or NHR5, R3 and R4 each independently represent =O or =NR5, and R5 represents a hydrogen atom or an alkyl group which may have substituents. The alkyl group represented by R5 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic, with linear being preferred. Examples of substituents include halogen atoms, hydroxyl groups, alkoxy groups, cyano groups, and amino groups.

[0021] In general formula (1), R1 and R2 are preferably OH groups. Also, R3 and R4 are preferably O groups.

[0022] In general formula (1), Me is a metal ion selected from the group consisting of Ni, Zn, Cu, Al, Fe, Co, and Mn (hereinafter also referred to as a specific metal ion).

[0023] Me is preferably Ni and at least one metal ion selected from the group consisting of Zn, Cu, Al, Fe, Co, and Mn, more preferably Ni and Zn or Cu, and particularly preferably Ni and Zn.

[0024] The molar ratio of at least two metal azo compounds with different metal species, selected from the group consisting of metal azo compounds represented by general formula (1) and metal azo compounds with tautomer structures thereof, can be calculated from the molar ratio of metal atoms. The molar ratio of metal azo compounds is preferably 97:3 to 10:90 for Ni and Zn or Cu, and more preferably 90:10 to 10:90. Furthermore, the total amount of metal ions, which are Ni, Zn, and Cu, is preferably 95 to 100 mol% per mole of all metal ions.

[0025] Embodiments containing at least two specific metal ions include embodiments in which at least two specific metal ions are contained in a common crystal lattice, and embodiments in which one type is contained in each of separate crystal lattices. Among these, the embodiment in which at least two specific metal ions are contained in a common crystal lattice is preferred. Whether the embodiment contains at least two specific metal ions in a common crystal lattice or one type is contained in each of separate crystal lattices can be determined, for example, by the X-ray diffraction method described in Japanese Patent Application Publication No. 2014-12838.

[0026] In general formula (1), Me may include metal ions other than the specified metal ions. Examples of metal ions other than the specified metal ions include Li, Cs, Mg, Na, K, Ca, Sr, Ba, La, Pr, Nd, Cd, Zr, Ce, etc.

[0027] General formula (2) [ka]

[0028] In general formula (2), the three R6 atoms each independently represent a hydrogen atom or an alkyl group which may have substituents. The alkyl group has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The alkyl group can be linear, branched, or cyclic, with linear being preferred. Examples of substituents include halogen atoms, hydroxyl groups, alkoxy groups, cyano groups, and amino groups.

[0029] In general formula (2), R6 is preferably a hydrogen atom.

[0030] The content of the compound represented by general formula (2) is preferably 0.1 to 4 moles, and more preferably 0.5 to 2 moles, of 1 mole of two or more metal azo compounds of at least different metal species selected from the group consisting of the metal azo compound represented by general formula (1) and metal azo compounds of tautomerized structures thereof.

[0031] The coloring agent (A1) is preferably formed by forming an adduct between a compound represented by general formula (2) and at least two or more metal azo compounds of different metal species selected from the group consisting of a metal azo compound represented by general formula (1) and a metal azo compound with a tautomer structure thereof. An adduct means a molecular aggregate. The bonds between these molecules may be due to, for example, intermolecular interactions, Lewis acid-base interactions, coordination bonds, or chain bonds. The adduct may also have a structure like an inclusion compound in which the guest molecule is incorporated into the lattice constituting the host molecule. The adduct may also have a structure like a composite intercalated crystal. A composite intercalated crystal is a chemically non-stoichiometric crystalline compound consisting of at least two elements. The adduct may also be a mixed substitution crystal in which two substances form a cocrystal and atoms of the second component are located in the regular lattice positions of the first component.

[0032] Examples of colorants (A1) include pigments described in Japanese Patent Publication No. 2014-12838, Japanese Patent Publication No. 2017-171912, Japanese Patent Publication No. 2017-171913, Japanese Patent Publication No. 2017-171914, Japanese Patent Publication No. 2017-171915, Japanese Patent Publication No. 2022-61494, etc.

[0033] The content of the coloring agent (A1) is preferably 1 to 80% by mass, and more preferably 5 to 75% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0034] (Coloring agent (A2)) Coloring agent (A) may contain coloring agents other than coloring agent (A1) (hereinafter also simply referred to as coloring agent (A2)).

[0035] The coloring agent (A2) is not particularly limited and may be any known pigment or dye, and can be used in combination.

[0036] (Pigment) The pigments are not particularly limited; for example, compounds classified as pigments in the color index can be used.

[0037] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179 ,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259, Examples include pigments 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, pigments described in Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, and the like.

[0038] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0039] Yellow pigments include, for example, 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 Examples include pigments described in JP 2012-226110, 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.

[0040] 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, 63, etc.

[0041] 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.

[0042] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0043] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0044] Other examples of inorganic pigments include silica, titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0045] It is preferable to use the pigment after it has been finely milled. The milling method is not particularly limited, and for example, wet milling, dry milling, or dissolution milling can all be used. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the finely milled pigment, as determined by TEM (transmission electron microscopy), is preferably 5 to 90 nm. However, from the viewpoint of dispersibility and contrast ratio, an average primary particle size of 10 to 70 nm is more preferable.

[0046] Resin may be added to the salt milling process as needed. By adding resin, the pigment is coated with resin, improving stability, lightfastness, etc. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in organic solvents. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

[0047] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, derivatives of these dyes, or lake pigments obtained by lake-forming dyes, can also be used.

[0048] Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Direct dyes preferably form salt compounds with an inorganic salt of the acid dye, or with an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, tertiary amine compound, secondary amine compound, or primary amine compound. Salt compounds that are salts of a resin component having these functional groups and an acid dye are also preferred. Furthermore, by sulfonamidating the salt compound to a sulfonic acid amide compound, it is easy to obtain a photosensitive composition with excellent resistance (lightfastness, solvent resistance). Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent resistance (light resistance and solvent resistance). The compound containing the onium base is preferably a resin having a cationic group.

[0049] Basic dyes can be used as is, but salt compounds formed by chlorinating with organic acids, perchloric acid, or their metal salts are preferred. Salt compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in salt compounds of basic dyes, preferred anionic components that act as counterions are salt compounds formed by chlorinating with organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid with a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt compound is further improved if it contains polymerizable unsaturated groups in its molecule.

[0050] Examples of dyes include azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes and indophenol dyes), dipyromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, and anthrapyridone dyes), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes), and quinoneimine dyes (such as oxazine dyes and thiazine dyes). Examples include azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes, as well as metal complex dyes based on these. Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred in terms of color characteristics such as hue, difficulty in color separation, and color unevenness, with xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes being more preferred.

[0051] The coloring agent (A2) can be used alone or in combination of two or more types.

[0052] When a green-coloring agent (A2) is used as the coloring agent (A2), the content of the green-coloring agent (A2) is preferably 5 to 95 parts by mass per 100 parts by mass of coloring agent (A1). The green-coloring agent (A2) is preferably CI Pigment Green 7, 36, 58, 59, or 63.

[0053] When a red-colored colorant (A2) is used as the coloring agent (A2), the content of the red-colored colorant (A2) is preferably 5 to 95 parts by mass per 100 parts by mass of colorant (A1). The red-colored colorant (A2) is preferably CI Pigment Red 177, 254, 269, 272, 291, or 296.

[0054] The content of the coloring agent (A) is preferably 1 to 80% by mass, and more preferably 5 to 75% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0055] [Alkali-soluble resin (B)] The photosensitive composition of the present invention comprises an alkali-soluble resin (B).

[0056] The alkali-soluble resin (B) can be any resin that dissolves in an alkaline developer, and known resins can be used. Examples include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamide-imide resin, and cyclic olefin resin.

[0057] The weight-average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 3,000 to 50,000, and more preferably 4,000 to 40,000.

[0058] The acid value of the alkali-soluble resin (B) is preferably 30 to 200 mg KOH / g, and more preferably 40 to 180 mg KOH / g.

[0059] Alkali-soluble resin (B) can be used alone or in combination of two or more types.

[0060] The alkali-soluble resin (B) is preferably present in an amount of 1 to 90% by mass, and more preferably 5 to 80% by mass, of 100% by mass of the non-volatile content of the photosensitive composition.

[0061] (Alkali-soluble resin (B1)) From the viewpoint of residual film properties and solvent resistance, the alkali-soluble resin (B) preferably contains an alkali-soluble resin (B1) (hereinafter also simply referred to as alkali-soluble resin (B1)) having alicyclic hydrocarbon-containing monomer units (b1) and polymerizable unsaturated group-containing monomer units (b2). The highly hydrophobic and rigid alicyclic hydrocarbon structure can form a tough film, and furthermore, it is presumed that the presence of polymerizable unsaturated groups allows for crosslinking of the resins upon exposure, resulting in a film with good residual film properties and solvent resistance.

[0062] Examples of alkali-soluble resins (B1) include copolymers of a monomer that forms an alicyclic hydrocarbon-containing monomer unit (b1) and a monomer that forms a polymerizable unsaturated group-containing monomer unit (b2), copolymers obtained by reacting a compound having a polymerizable unsaturated group with a copolymer of a monomer that forms an alicyclic hydrocarbon-containing monomer unit (b1) and another monomer copolymerizable therewith to introduce polymerizable unsaturated group-containing monomer units (b2), and copolymers obtained by the method described in Japanese Patent Application Publication No. 2008-165059.

[0063] [Alicyclic hydrocarbon-containing monomer unit (b1)] Monomers that form alicyclic hydrocarbon-containing monomer units (b1) include, for example, isobolonyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0064] From the viewpoint of residual film properties and solvent resistance, the content of alicyclic hydrocarbon-containing monomer units (b1) is preferably 1 to 60 mol%, and more preferably 1 to 40 mol%, of the total constituent units of the alkali-soluble resin (B1).

[0065] [Polymerizable unsaturated group-containing monomer unit (b2)] Methods for incorporating polymerizable unsaturated group-containing monomer units (b2) into an alkali-soluble resin (B1) include, for example, the methods (i) to (iii) shown below.

[0066] <Method (i)> Method (i) involves, for example, first polymerizing an epoxy group-containing monomer and other monomer polymers (precursors). Then, a carboxyl group-containing monomer (modified compound) is added to the epoxy group of the precursor.

[0067] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0068] Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among these, acrylic acid and methacrylic acid are preferred.

[0069] From the viewpoint of developability, a site in which an acid anhydride is reacted with an epoxy group of a carboxyl group-containing monomer to an epoxy group of an epoxy group-containing monomer unit is also preferred as a polymerizable unsaturated group-containing monomer unit (b2).

[0070] Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0071] <Method (ii)> Method (ii) involves, for example, first polymerizing a polymer (precursor) of a carboxyl group-containing monomer and other monomers. Then, an epoxy group-containing monomer (modified compound) is added to the carboxyl group of the precursor.

[0072] <Method (iii)> Method (iii) involves, for example, first polymerizing a polymer (precursor) of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Then, reacting the hydroxyl group of the precursor with the isocyanate group of an isocyanate group-containing monomer (modified compound).

[0073] Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate.

[0074] Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0075] From the viewpoint of residual film properties and solvent resistance, the content of polymerizable unsaturated group-containing monomer units (b2) is preferably 5 to 80 mol%, and more preferably 10 to 80 mol%, of the total constituent units of the alkali-soluble resin (B1).

[0076] [Monomer units (b3) whose homopolymer glass transition temperature is 0°C or lower] From the viewpoint of cross-sectional shape, the alkali-soluble resin (B1) more preferably has monomer units (b3) whose homopolymer glass transition temperature is 0°C or lower. Particularly preferred is monomer units (b3) whose homopolymer glass transition temperature is -30°C or lower. A homopolymer is a single polymer of each monomer, and the glass transition temperature values ​​used are those shown in Brandrup, J. Immergut, EH., "Polymer Handbook, Third edition, John Wiley & Sons, 1989".

[0077] Monomers that form monomer units (b3) with a homopolymer glass transition temperature of 0°C or lower include, for example, phenoxyethyl acrylate (-22°C), lauryl acrylate (-3°C), 2-ethylhexyl acrylate (-50°C), n-hexyl acrylate (-57°C), n-butyl acrylate (-48°C), isobutyl acrylate (-40°C), ethyl acrylate (-24°C), lauryl methacrylate (-65°C), n-hexyl methacrylate (-5°C), 2-ethylhexyl methacrylate (-10°C), 2-methoxyethyl acrylate (-50°C), tetrahydrofurfuryl acrylate (-12°C), 2-hydroxyethyl acrylate (-15°C), and 4-hydroxybutyl acrylate (-60°C). Among these, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferred.

[0078] From the viewpoint of cross-sectional shape, the content of monomer units (b3) of homopolymers with a glass transition temperature of 0°C or lower is preferably 1 to 50 mol%, and more preferably 5 to 40 mol%, of the total constituent units of the alkali-soluble resin (B1).

[0079] [Other monomer units (b4)] Alkali-soluble resin (B1) may contain monomer units other than (b1) to (b3) (hereinafter also simply referred to as other monomer units (b4)).

[0080] Other monomers that form monomer units (b4) include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, benzyl (meth)acrylate, and paracumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate; Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl methacrylate, and glycerin monomethacrylate; Epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; Vinyl fatty acids such as vinyl acetate and vinyl propionate; Blocked isocyanate group-containing acrylates such as 2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, 2-(3,5-diethylpyrazole-1-yl)carbonylaminoethyl methacrylate, and 2-[O-(1'-methylpropyrideneamino)carboxyamino]ethyl methacrylate; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl) N-substituted maleimides such as maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimidacridine; 2-(meth)acryloyloxyethyl acid phosphate, phosphate ester group-containing (meth)acrylates such as compounds obtained by reacting the hydroxyl group of the hydroxyl group-containing (meth)acrylate mentioned above with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate; Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. These monomers can be used individually or in combination of two or more.

[0081] Alkali-soluble resin (B1) can be used alone or in combination of two or more types.

[0082] The content of alkali-soluble resin (B1) is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, of 100% by mass of alkali-soluble resin (B).

[0083] (Alkali-soluble resin (B2)) The photosensitive composition of the present invention may contain an alkali-soluble resin (B2) other than alkali-soluble resin (B1) (hereinafter also simply referred to as alkali-soluble resin (B2)) as the alkali-soluble resin (B).

[0084] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0085] Polymerizable compound (C) is not particularly limited and includes known compounds. Examples include monomers and oligomers having polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups with ethylenically unsaturated double bonds. Examples of polymerizable compound (C) include lactone-modified polymerizable compounds (C1), polymerizable compounds having acidic groups (C2), polymerizable compounds having hydroxyl groups (C3), polymerizable compounds having urethane bonds (C4), polymerizable compounds having a tertiary amine structure (C5), polymerizable compounds having a dendrimer structure or hyperbranch structure (C6), and other polymerizable compounds (C7).

[0086] (Lactone-modified polymerizable compound (C1)) From the viewpoint of solvent resistance, the polymerizable compound (C) preferably contains a lactone-modified polymerizable compound (C1).

[0087] Lactone-modified polymerizable compounds (C1) are compounds having a structure modified with lactone within the molecule. Lactone-modified polymerizable compounds are obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound (C1) is preferably a compound represented by the following general formula (4).

[0088] General formula (4) [ka]

[0089] In general formula (4), all six Rs are groups represented by general formula (5) below, or one to five of the six Rs are groups represented by general formula (5) below, and the remaining ones are groups represented by general formula (6) below.

[0090] General formula (5) [ka]

[0091] In general formula (5), R 1 represents a hydrogen atom or a methyl group, m is an integer between 1 and 2, and * is a bond that connects to the oxygen atom in general formula (4).

[0092] General formula (6) [ka]

[0093] In general formula (6), R 1 represents a hydrogen atom or a methyl group, and * represents a bond that connects to the oxygen atom in general formula (4).

[0094] Lactone-modified polymerizable compounds (C1) are commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. For example, DPCA-20 (where m=1 in general formulas (4) to (16), the number of groups represented in general formula (5) = 2, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-30 (in general formulas (4) to (6), m=1, number of groups represented in general formula (5)=3, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-60 (in general formulas (4) to (16), m=1, number of groups represented in general formula (5)=6, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-120 (in general formulas (4) to (6), m=2, number of groups represented in general formula (5)=6, R 1 Examples include compounds in which all atoms are hydrogen atoms.

[0095] Lactone-modified polymerizable compounds (C1) are, from the viewpoint of solvent resistance, characterized in general formulas (4) to (6) by m=1, the number of groups represented in general formula (5) = 2 to 6, and R 1 Compounds in which all atoms are hydrogen atoms are preferred, and in general formulas (4) to (6), m=1, the number of groups represented in general formula (5) = 2 or 3, R 1 Compounds in which all atoms are hydrogen atoms are more preferable.

[0096] Lactone-modified polymerizable compounds (C1) can be used alone or in combination of two or more types.

[0097] The content of the lactone-modified polymerizable compound (C1) is preferably 5 to 90% by mass, and more preferably 10 to 85% by mass, based on 100% by mass of polymerizable compound (C).

[0098] (Polymerizable compound (C2) containing an acidic group) From the viewpoint of pattern formation, polymerizable compound (C) preferably contains polymerizable compound (C2) having an acidic group.

[0099] Examples of polymerizable compounds (C2) having an acidic group include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among these, carboxyl groups are preferred. Examples of polymerizable compounds (C2) having an acidic group include esters of polyhydric alcohols and (meth)acrylic acid poly(meth)acrylates containing free hydroxyl groups and dicarboxylic acids; and esters of polyhydric acids and monohydroxyalkyl (meth)acrylates. Note that polymerizable compounds (C2) having an acidic group are compounds that do not have a urethane bond.

[0100] Examples of the polyhydric alcohols mentioned above include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0101] Examples of the dicarboxylic acids mentioned above include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0102] Examples of the polycarboxylic acids mentioned above include trimellitic acid and pyromellitic acid.

[0103] Examples of the above monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0104] Examples of commercially available polymerizable compounds (C2) containing acidic groups include Viscoat #2500P from Osaka Organic Chemical Industry Co., Ltd., Aronics M-5300, M-5400, M-5700, M-510, M-520, and M-521 from Toagosei Co., Ltd., Light Acrylate HOA-MS(N), HOA-HH(N), HOA-MPE(N), and P-1A(N) from Kyoeisha Chemical Co., Ltd., and β-CEA from Daicel Ornex Co., Ltd.

[0105] The content of the polymerizable compound (C2) having an acidic group is preferably 5 to 90% by mass, and more preferably 10 to 85% by mass, based on 100% by mass of polymerizable compound (C).

[0106] (Molybdenum-containing polymerizable compound (C3)) Polymerizable compounds (C3) having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric acid EO, or Examples include acrylic acid esters such as PO-modified (meth)acrylate, isocyanuric acid EO or PO-modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO-modified penta(meth)acrylate, and dipentaerythritol caprolactone-modified penta(meth)acrylate, as well as epoxy(meth)acrylate obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid. Among these, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred.

[0107] Examples of commercially available polymerizable compounds (C3) containing hydroxyl groups include KAYARAD R-128H and R-167 from Nippon Kayaku Co., Ltd., Bremmer GLM, GLM-R, GMR-M, GMR-R, GAM, GAM-R, and G-FA80 from NOF Corporation, Aronix M-5700 and M-920 from Toagosei Co., Ltd., NK Ester 701A from Shin Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P from Kyoeisha Chemical Co., Ltd., and Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A from Osaka Gas Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 from Osaka Gas Chemical Co., Ltd.

[0108] (Polymerizable compound (C4) containing urethane bonds) Polymerizable compounds (C4) having a urethane bond include, for example, urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting it with a hydroxyl group-containing (meth)acrylate.

[0109] Examples of the hydroxyl group-containing (meth)acrylates mentioned above include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0110] Examples of the polyfunctional isocyanates mentioned above include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate, as well as their bilets, isocyanate nulates, and trimethylolpropane adducts.

[0111] Polymerizable compounds (C4) having urethane bonds may also have acidic groups. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups. Among these, carboxyl groups are preferred.

[0112] One method for introducing an acidic group into a polymerizable compound (C4) having a urethane bond is to first react the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then add a mercapto compound having a carboxyl group to the product.

[0113] Examples of mercapto compounds having the carboxyl group mentioned above include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0114] Examples of commercially available polymerizable compounds (C4) containing urethane bonds include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G from Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA from Shin Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 from Daicel Ornex Co., Ltd.

[0115] (A polymerizable compound (C5) having a tertiary amine structure) Polymerizable compounds (C5) having a tertiary amine structure include, for example, tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and Michael addition reaction products of (meth)acrylate compounds (X) and amine compounds (Y).

[0116] (Meth)acrylate compound (X) is, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin Examples include lint tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri and tetra(meth)acrylate, diglycerin alkylene oxide-modified tri and tetra(meth)acrylate, and dipenerythritol alkylene oxide-modified tetra, penta, and hexa(meth)acrylate. Examples of alkylene oxide units in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. Furthermore, (meth)acrylate compounds (X) can also include (meth)acrylate compounds having an acidic group.

[0117] (Meth)acrylate compound (X) can be used alone or in combination of two or more types.

[0118] Amine compound (Y) is a primary amine such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, p-aminophenol, etc. Examples include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilynphenol, 4-anilynphenol, and other secondary amines.

[0119] Amine compound (Y) can be used alone or in combination of two or more types.

[0120] There are no particular limitations on the method for producing the Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y), and known methods can be used. For example, the methods described in International Publication No. 2006 / 075754, Japanese Patent Publication No. 2008-545859, and Japanese Patent Application Publication No. 2017-066347 can be cited.

[0121] A polymerizable compound (C5) having a tertiary amine structure may have an acidic group and / or a hydroxyl group. Methods for introducing an acidic group and / or a hydroxyl group include, for example, using a compound having an acidic group and / or a hydroxyl group with a (meth)acrylate compound (X) or an amine compound (Y), or adding an acid anhydride after a Michael addition reaction.

[0122] Examples of commercially available polymerizable compounds (C5) having a tertiary amine structure include Aronics MT-3041 and MT-3042 manufactured by Toagosei Co., Ltd.

[0123] (Polymerizable compounds (C6) having a dendrimer structure or hyperbranch structure) Polymerizable compounds having a dendrimer structure have a chemical structure in which a core (hereinafter also referred to as the core portion) repeatedly branches outwards in a regular manner, with polymerizable unsaturated groups bonded to the ends of these branches. They have a highly controlled spherical chemical structure and molecular weight. Hyperbranched structures have a chemical structure similar to that of dendrimer structures.

[0124] Examples of commercially available polymerizable compounds (C6) having a dendrimer or hyperbranched structure include Viscoat #1000LT (dendrimer structure, average acryloyl group count 14) from Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average acryloyl group count 18) and Miramer SP-1108 (dendrimer structure, average acryloyl group count 13) from Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average acryloyl group count 9), CN2302 (hyperbranched structure, average acryloyl group count 16), CN2303 (hyperbranched structure, average acryloyl group count 6), and CN2304 (hyperbranched structure, average acryloyl group count 18) from SARTOMER, and Eternal Examples include Etercure6361-100 (hyperbranch structure, average acryloyl group count 8), Etercure6362-100 (hyperbranch structure, average acryloyl group count 12), Etercure6363 (hyperbranch structure, average acryloyl group count 16), and EtercureDR-E522 (hyperbranch structure, average acryloyl group count 15), all manufactured by Materials Inc.

[0125] (Other polymerizable compounds (C7)) Other polymerizable compounds (C7) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (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, glycerol tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified or PO-modified tri(meth)acrylate Examples include di(meth)acrylate, isocyanuric acid EO-modified or PO-modified tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl(meth)acrylate, various acrylic acid esters and methacrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0126] Other commercially available polymerizable compounds (C7) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, D-310 from Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, M-211B from Toagosei Co., Ltd. M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, M-930, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 from Osaka Organic Chemical Industry Co., Ltd., and OGSOL from Osaka Gas Chemical Co., Ltd. Examples include EA-0200, EA-0300, Miramer HR6060, 6100, 6200 from Miwon Specialty Chemical Co., Ltd., and NK esters A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, AD-TMP from Shin Nakamura Chemical Industry Co., Ltd.

[0127] Polymerizable compound (C) can be used alone or in combination of two or more types.

[0128] The content of polymerizable compound (C) is preferably 5 to 70% by mass, and more preferably 5 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0129] [Polymerization initiator (D)] (Oxime in one molecule) ester Polymerization initiator having two groups (D1) The photosensitive composition of the present invention contains an oxime as the polymerization initiator (D) in one molecule. ester It contains a polymerization initiator (D1) having two groups.

[0130] The polymerization initiator (D1) having two oxime groups in one molecule has no particular limitation, and known compounds can be used. For example, compounds described in JP-A-2005-215378, JP-A-2011-105713, JP-T-2017-523465, JP-A-2021-011486, etc. can be mentioned. Among them, the compound represented by the following general formula (3) is preferable. ester In the general formula (3), X

[0131] General formula (3)

Chemical formula

[0132] In the general formula (3), X 1 and X 2 each independently represents -CO- (carbonyl bond) or a single bond. X 3 represents a single bond or a sulfur atom. R 1 represents an alkyl group having 1 to 20 carbon atoms, R 2 and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic ring having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R 4 and R 5 each independently represents an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. Two R 6 each independently represents a hydrogen atom or a nitro group.

[0133] In the general formula (3), X 1 and X 2 each independently represents -CO- (carbonyl bond) or a single bond. Among them, from the viewpoint of solubility in an organic solvent, at least one of X 1 and X 2 is preferably -CO-, and more preferably both are -CO-.

[0134] In the general formula (3), X3 This represents a single bond or a sulfur atom. Of these, a single bond is preferred.

[0135] In general formula (3), R 1 This represents an alkyl group with 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group. Among these, ethyl group, propyl group, and isopropyl group are preferred.

[0136] In general formula (3), R 2 and R 3 Each of these independently represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, a heterocycle with 2 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an arylalkyl group with 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group. Among these, pentyl group, hexyl group, heptyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group are preferred. Examples of heterocyclic groups having 2 to 30 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups. The aryl group may also be a group substituted with a halogen atom, an amino group, a nitro group, etc. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl groups. The arylalkyl group may also be a group substituted with a halogen atom, an amino group, a nitro group, etc. Among these, R 2 and R 3 From the viewpoint of solubility in organic solvents, it is preferable that at least one of the members is a linear alkyl group having 1 to 20 carbon atoms, and from the viewpoint of solubility in organic solvents and suppression of water stains, it is more preferable that one member is a linear alkyl group having 1 to 20 carbon atoms and the other is a cyclic alkyl group having 1 to 20 carbon atoms.

[0137] In general formula (3), R 4 and R 5 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, cyclopentyl group, cyclopentylmethyl group, and cyclohexyl group. Among these, methyl group, ethyl group, propyl group, and isopropyl group are preferred from the viewpoint of reactivity. Examples of heterocyclic groups having 2 to 30 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups. The aryl group may also be substituted with a halogen atom, an amino group, a nitro group, etc. Among these, the phenyl group is preferred from the viewpoint of reactivity. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl groups. The arylalkyl group may also be a group substituted with a halogen atom, an amino group, a nitro group, etc. Among these, R 4 and R 5 From the viewpoint of reactivity, a methyl group, an ethyl group, or a phenyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0138] In general formula (3), two R 6 Each of these independently represents either a hydrogen atom or a nitro group. Of these, the hydrogen atom is preferred.

[0139] The method for producing the compound represented by general formula (3) is not particularly limited, and known methods can be used. For example, the methods described in Japanese Patent Publication No. 2017-523465 and Japanese Patent Application Publication No. 2021-011486 can be used.

[0140] The following are oximes in one molecule. ester Specific examples of polymerization initiators (D1) having two groups are shown. However, the present invention is not limited to these examples.

[0141] [ka]

[0142] Oxime in one molecule ester Polymerization initiators (D1) containing two groups can be used alone or in combination of two or more types.

[0143] Oxime in one molecule ester The content of the polymerization initiator (D1) containing two groups is preferably 30 to 100% by mass, and more preferably 40 to 100% by mass, of the polymerization initiator (D) by mass.

[0144] (Other polymerization initiators (D2)) Polymerization initiator (D) contains oxime in one molecule. ester It is preferable to include a polymerization initiator (D2) other than the polymerization initiator (D1) having two groups (hereinafter also simply referred to as "other polymerization initiator (D2)").

[0145] Other polymerization initiators (D2) are not particularly limited, and known compounds can be used. For example, compounds that generate radicals by the action of light or heat to initiate or promote radical polymerization reactions can be used. A polymerization initiator that generates radicals in response to light (hereinafter also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals in response to light from ultraviolet to visible light. A polymerization initiator that generates radicals by heat (hereinafter also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0146] Examples of photopolymerization initiators include acetophenone compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(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, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole3-yl]-,1-(O-acetyl oxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; and carbazole compounds.

[0147] Commercially available products include acetophenone compounds such as Omnirad907, 369E, 379EG, 127, 184, 1173, and 2959 from IGM Resins; acylphosphine compounds such as Omnirad819 and TPO from IGM Resins; oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 from BASF Japan; ADEKA's ADEKA Arcules N-1919T, NCI-730, NCI-831E, and NCI-930; and TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, and 3057 from Changzhou Strong New Materials Co., Ltd. Examples include Omnirad 1312, 1314, and 1316 from Resins, SPI-02, 03, 04, 06, and 07 from Samyang Corporation, and DFI-020, 306, and EOX-01 from Daito Chemix. Also, compounds described in Japanese Patent Publication No. 2007-210991, 2009-179619, 2010-037223, 2010-215575, 2011-020998, International Publication No. 2015 / 036910, Japanese Patent Publication No. 2019-507108, Japanese Patent Publication No. 2019-528331, and International Publication No. 2021 / 175855 are also examples.

[0148] Examples of thermal polymerization initiators include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. Pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; Azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples include organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic acid peroxide, and benzoyl peroxide.

[0149] Other polymerization initiators (D2) can be used alone or in combination of two or more types.

[0150] The content of polymerization initiator (D) is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0151] [Thermosetting compound (E)] The photosensitive composition of the present invention preferably contains a thermosetting compound (E) from the viewpoint of solvent resistance. This is because the thermosetting compound (E) reacts during the heating process, increasing the crosslinking density and thus improving resistance.

[0152] The thermosetting compound (E) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of thermosetting compounds (E) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds, oxetane compounds, and melamine compounds are preferred, and epoxy compounds are more preferred.

[0153] (Epoxy compound (E1)) Epoxy compounds (E1) include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene) and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene Examples include polymers of divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins obtained by glycidylating alcohols, etc.

[0154] Commercially available epoxy compounds (E1) include, for example, Epicote 807, 815, 825, 827, 828, 190P, and 191P from Shell Epoxy Corporation, and TECHMORE from Mitsui Chemicals. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 from Nippon Kayaku Co., Ltd., Epicote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 from Japan Epoxy Resin Co., Ltd., Celoxide 2021, EHPE-3150, Epolid GT401 from Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 from Nagase ChemteX Corporation, TEPIC-L, H, S from Nissan Chemical Industries, Ltd., EPICLON from DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500, etc.

[0155] The epoxy compound (E1) is preferably a compound having 2 to 50 epoxy groups in its molecule, and more preferably a compound having 10 to 30 epoxy groups. Furthermore, the epoxy compound (E1) is preferably an epoxy compound having an aromatic ring and / or an aliphatic ring, and more preferably an epoxy compound having an aliphatic ring. The epoxy groups are preferably bonded to the aromatic ring and / or aliphatic ring via single bonds or linking groups. Examples of linking groups include alkyl groups, arylene groups, -O-, -NR- (where R represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group), -SO2-, -CO-, -O-, and -S-. In the case of a structure having an aliphatic ring, it is more preferable that the epoxy groups are bonded to the aliphatic ring via single bonds.

[0156] The epoxy equivalent of epoxy compound (E1) is preferably 50 to 400 g / eq, and more preferably 100 to 200 g / eq. Note that epoxy equivalent is defined as the mass of the epoxy compound containing one equivalent of epoxy groups.

[0157] Epoxy compounds having an aliphatic ring include, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-methadioxane, bis(3, Examples include 4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl carboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexane carboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone, and 1,2-epoxy-4-(2-oxyranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol.

[0158] Epoxy compounds having an aliphatic ring preferably include compounds represented by the following general formula (7).

[0159] General formula (7) [ka]

[0160] In general formula (7), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m is an integer from 1 to 6, and n is an integer from 1 to 30.

[0161] R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol. The group obtained by removing m hydroxyl groups from an m-valued alcohol is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, cyclic, or a combination of these. Examples of alkyl groups having 2 to 20 carbon atoms include ethyl group, methyl group, propyl group, isopropyl group, 2,2-dimethylpropyl group, butyl group, isobutyl group, tert-butyl group, 3,3-dimethylbutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group. Among these, branched alkyl groups having 3 to 12 carbon atoms are more preferred.

[0162] m represents an integer between 1 and 6, and n represents an integer between 1 and 30. When m is 2 or greater, the n in each of the bases in parentheses in general formula (7) may be the same or different.

[0163] Compounds represented by general formula (7) specifically include the 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available examples include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0164] Epoxy compounds (E1) can be used alone or in combination of two or more types.

[0165] The content of epoxy compound (E1) is preferably 0.5 to 20% by mass, and more preferably 1 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0166] (Oxetane compound (E2)) Oxetane compounds (E2) are known compounds having an oxetane group. Examples of oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or multifunctional oxetane compounds.

[0167] Examples of monofunctional oxetane compounds include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 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.

[0168] Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

[0169] Examples of bifunctional oxetane compounds 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 glycos(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl(3-ethyl- Examples include 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

[0170] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0171] Examples of oxetane compounds with three or more functionalities include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipenta Examples include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0172] The content of the oxetane compound (E2) is preferably 0.5 to 20% by mass, and more preferably 1 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0173] (Melamine compound (E3)) Melamine compound (E3) is a compound having a melamine ring structure. Melamine compound (E3) is preferably a compound having a methylol group.

[0174] Examples of commercially available products include Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 from Nippon Cytec Industries Co., Ltd.

[0175] The content of melamine compound (E3) is preferably 0.5 to 20% by mass, and more preferably 1 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0176] Thermosetting compound (E) can be used alone or in combination of two or more types.

[0177] [Hardening agent (hardening accelerator)] The photosensitive composition of the present invention may be used in combination with a curing agent (curing accelerator) to assist in the curing of the thermosetting compound (E). Examples of curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Examples of curing agents include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct, etc.).

[0178] The hardening agent can be used alone or in combination of two or more types.

[0179] The curing agent content is preferably 0.01 to 15 parts by mass per 100 parts by mass of thermosetting compound (E).

[0180] [Sensitizer (F)] The photosensitive composition of the present invention may contain a sensitizer (F).

[0181] The sensitizer (F) is not particularly limited, and known compounds can be used. For example, chalcone compounds, unsaturated ketones represented by dibenzalacetone, 1,2-diketone compounds represented by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, polymethine dyes such as oxonol compounds, acridine compounds, azine compounds, thiaidine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, sucrose compounds, etc. Examples include allyllium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyradinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxaliloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyririum compounds, thiopyrillium compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospilopyran compounds, metal arene complexes, organoruthenium complexes, or benzophenone compounds. Among these, thioxanthone compounds and benzophenone compounds are preferred from the viewpoint of pattern formation.

[0182] (Thioxanthone compounds) Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Among these, 2,4-diethylthioxanthone is preferred.

[0183] (Benzophenone compounds) Examples of benzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0184] The sensitizer (F) can be used alone or in combination of two or more types.

[0185] The content of the sensitizer (F) is preferably 5 to 200 parts by mass, and more preferably 10 to 150 parts by mass, per 100 parts by mass of the polymerization initiator (D).

[0186] [Dye derivative (G)] The photosensitive composition of the present invention may contain a dye derivative (G).

[0187] Dye derivatives (G) are compounds having acidic groups, basic groups, neutral groups, etc., on organic dye residues. Examples of dye derivatives (G) include compounds having acidic substituents such as sulfo groups, carboxyl groups, and phosphate groups, as well as their amine salts, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminal, and compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0188] Specifically, diketopyrrolopyrrole dye derivatives include JP 2001-220520, International Publication No. 2009 / 081930, International Publication No. 2011 / 052617, International Publication No. 2012 / 102399, and JP 2017-156397; phthalocyanine dye derivatives include JP 2007-226161, International Publication No. 2016 / 163351, JP 2017-165820, and Patent No. 5753266; and anthraquinone dye derivatives include JP Sho 63-264 Japanese Patent Publication No. 674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, International Publication No. 2009 / 025325, as quinacridone-based dye derivatives, Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, as dioxazine-based dye derivatives, Japanese Patent Publication No. 2011-162662, as thiaidine-indigo-based dye derivatives, Japanese Patent Publication No. 2007-314785, triazine Examples of benzoindole-based dye derivatives include Japanese Patent Publication No. 61-246261, Japanese Patent Publication No. 11-199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, and Japanese Patent Publication No. 2007-314681. Examples of benzoisoindole-based dye derivatives include Japanese Patent Publication No. 2009-57478. Examples of quinophthalone-based dye derivatives include Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, and Japanese Patent Publication No. 2012-226 Examples of known dye derivatives include those described in Japanese Patent Publication No. 110, Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439 as naphthol-based dye derivatives, Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092 as azo-based dye derivatives, Japanese Patent Publication No. 2004-307854 as an acidic substituent, and Japanese Patent Publication No. 2002-201377, Japanese Patent Publication No. 2003-171594, Japanese Patent Publication No. 2005-181383 and Japanese Patent Publication No. 2005-213404 as basic substituents.In addition, these documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but compounds having substituents such as acidic groups, basic groups, or neutral groups on the aforementioned organic dye residues are synonymous with dye derivatives.

[0189] Dye derivative (G) can be used alone or in combination of two or more types.

[0190] The content of the pigment derivative (G) is preferably 1 to 20 parts by mass, and more preferably 2 to 15 parts by mass, per 100 parts by mass of the coloring agent (A).

[0191] [Dispersion resin (H)] The photosensitive composition of the present invention may contain a dispersion resin (H).

[0192] The dispersion resin (H) is not particularly limited, and any known resin can be used. Examples of dispersion resins (H) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester systems, modified polyacrylate systems, ethylene oxide / propylene oxide adduct compounds, and phosphate ester systems.

[0193] The molecular structure of the dispersion resin (H) can be, for example, a random structure, a block structure, a graft structure, a comb structure, or a star structure. Among these, a block structure or a comb structure is preferred from the viewpoint of dispersion stability.

[0194] The dispersion resin (H) can be used alone or in combination of two or more types.

[0195] From the viewpoint of dispersion stability, the content of the dispersion resin (H) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the coloring agent (A).

[0196] (Dispersion resin with acidic groups (H1)) From the viewpoint of pattern-forming properties, the photosensitive composition of the present invention preferably contains a dispersion resin (H1) having an acidic group as the dispersion resin (H).

[0197] Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups. Among these, carboxyl groups and phosphate groups are preferred, with carboxyl groups being more preferred.

[0198] The dispersion resin (H1) having an acidic group is not particularly limited, and known resins can be used. Examples include polycarboxylic acid esters such as polyacrylate, polycarboxylic acids, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid SL copolymers, phosphate esters, etc. Also, resins described in Japanese Patent Publication No. 2007-23195, International Publication No. 2008 / 007776, Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2009-251481, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, etc.

[0199] Examples of commercially available dispersion resins (H1) having acidic groups include Disperbyk-101, 102, 103, 106, 110, 111, 118, 170, 171, 174, 2096, BYK-P104, BYK-P105, and BYK-220S from BIC Chemie Japan, and SOLSPERSE-3000, 21000, 26000, 36600, 41000, 41090, 43000, 45000, and 53095 from Lubrizol Nippon.

[0200] The acid value of the dispersion resin (H1) having an acidic group is preferably 20 to 250 mg KOH / g, and more preferably 30 to 200 mg KOH / g.

[0201] The dispersion resin (H1) having an acidic group can be used alone or in combination of two or more types.

[0202] (Dispersion resin containing basic groups (H2)) From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains a dispersion resin (H2) having a basic group as the dispersion resin (H).

[0203] Basic groups include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles and other groups containing nitrogen atoms.

[0204] The dispersion resin (H2) having a basic group is not particularly limited, and known resins can be used. Examples include salts of long-chain polyaminoamides and high molecular weight acid esters, polyester polyamines, amine salts of copolymers of unsaturated carboxylic acids such as polyacrylic acid, and polyethyleneimine compounds. Resins described in Japanese Patent Publication No. 2013-119568, Japanese Patent Publication No. 2018-203795, Japanese Patent Publication No. 2019-089953, Japanese Patent Publication No. 2019-089954, and International Publication No. 2020 / 031634 are also examples.

[0205] Commercially available dispersion resins (H2) containing basic groups include Disperbyk-108, 109, 161, 162, 164, 167, 168, 182, 184, 185, 2000, 2008, 2013, 2022, 2050, 2055, 2150, 2155, 2163, BYK-LPN6919, 21116 from BIC Chemie Japan, and SOL from Lubrizol Nippon Co., Ltd. Examples include SPERSE-9000, 13240, 13650, 13940, 17000, 18000, 24000SC, 24000GR, 28000, 31845, 32000, 32500, 34750, 35100, 35200, 36600, 38500, and Ajisper PA111, PB711, PB821, PB822, PB824 from Ajinomoto Fine Techno Co., Ltd.

[0206] The amine value of the dispersion resin (H2) having a basic group is preferably 20 to 250 mg KOH / g, and more preferably 30 to 150 mg KOH / g.

[0207] Dispersion resins (H2) having basic groups can be used alone or in combination of two or more types.

[0208] [Leveling agent (I)] The photosensitive composition of the present invention may contain a leveling agent (I).

[0209] Examples of leveling agents (I) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0210] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0211] Examples of commercially available silicone-based surfactants include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Bic Chemie, and FZ-70 from Toray Dow Corning. Examples include 02, 2110, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s 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.

[0212] Examples of fluorinated surfactants include compounds having fluorocarbon chains.

[0213] Examples of commercially available fluorine-based surfactants include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, as well as R-40-LM, R-41, RS-72-K, and DS-21 from DIC Corporation, FC-4430 and 4432 from Sumitomo 3M Corporation, EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Corporation.

[0214] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0215] Examples of commercially available nonionic surfactants include Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L1 20, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 1 Examples include 02, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical's (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95.

[0216] Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0217] Examples of commercially available cationic surfactants include Kao Corporation's Acetamine 24, Cotamine 24P, 60W, and 86P Concentrate.

[0218] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate esters, and the like.

[0219] Examples of commercially available anionic surfactants include Fagent 100 and 150 manufactured by Neos Co., Ltd., ADEKA Hope YES-25 manufactured by ADEKA Corporation, ADEKA Cole TS-230E, PS-440E, EC-8600, and the like.

[0220] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

[0221] Examples of commercially available amphoteric surfactants include Amhitole 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.

[0222] The leveling agent (I) can be used alone or in combination of two or more kinds.

[0223] The content of the leveling agent (I) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0224] [Organic solvent (J)] The photosensitive composition of the present invention can contain an organic solvent (J).

[0225] The organic solvent (J) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl Butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene Nzen, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. are mentioned.

[0226] From the environmental perspective, it is preferable that the photosensitive composition of the present invention substantially does not contain organic solvents that are aromatic hydrocarbons (such as toluene, xylene, benzene, chlorobenzene, etc.). Substantially not containing means that in the photosensitive composition, 50 mass ppm or less is preferable, 30 mass ppm or less is more preferable, and 10 mass ppm or less is even more preferable.

[0227] The organic solvent (J) can be used alone or in combination of two or more.

[0228] The content of the organic solvent (J) is preferably an amount such that the non-volatile content of the photosensitive composition is 5 to 70% by mass.

[0229] [Other components (K)] The photosensitive composition of the present invention may contain components (K) other than those described above (hereinafter simply referred to as "other components (K)"). Examples of other components (K) include curing agents, acid generators, curing catalysts, chain transfer agents, polymerization inhibitors, antioxidants, adhesion enhancers, ultraviolet absorbers, and near-infrared absorbers. The content of other components (K) can be appropriately set within a range that does not impair the effects of the present invention.

[0230] [Water content] From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains 2.0% by mass or less of water.

[0231] The water content in the photosensitive composition is more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less. Furthermore, the lower limit of the water content is preferable as much as possible, but there are no particular restrictions.

[0232] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, each of the above-mentioned components can be thoroughly dried to reduce the amount of water contained in the components before use. Other methods include manufacturing the photosensitive composition while blowing in dry air, an inert gas, or a mixture thereof, or adding molecular sieves after manufacturing to dehydrate the product.

[0233] The water content can be measured by known methods such as the Karl Fischer method.

[0234] [Method for producing a photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. During preparation, the components may be combined all at once, or they may be dissolved or dispersed in an organic solvent and then added sequentially. For example, a dispersion can be produced by adding a colorant (A), an alkali-soluble resin (B), and an organic solvent (J), and performing a dispersion treatment. Then, the dispersion can be mixed with a polymerizable compound (C), a polymerization initiator (D), etc. The components to be added and the timing of their addition are arbitrary. Furthermore, the dispersion process can be performed multiple times.

[0235] Examples of distributed processing machines include two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0236] The average dispersed particle size (secondary particle size) of the colorant (A) in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

[0237] The method for measuring the average dispersed particle diameter (secondary particle diameter) uses, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power-spectrum method), with particle permeability set to absorption mode, particle shape to non-spherical, and D50 particle diameter as the average diameter. The diluent solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure immediately after sample preparation of ultrasonically treated samples to obtain results with less variation.

[0238] The photosensitive composition is preferably subjected to centrifugation, sintering filter filtration or membrane filter filtration to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, more preferably 0.5 μm or larger, and any mixed dust. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0239] <Membrane> The film of the present invention is formed using the photosensitive composition described above. While a patterned film is preferred, it can also be used as a flat film.

[0240] [Memory manufacturing method] The method for manufacturing the film is not particularly limited, and known methods can be used. For example, it can be manufactured by a process of coating the photosensitive composition of the present invention onto a substrate.

[0241] The substrate may be, for example, a substrate made of materials such as glass, resin, silicon, etc. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or CMOS may be formed on the substrate. Further, a primer layer may be provided on the substrate as needed for improving adhesion to the upper layer, preventing diffusion of substances, and planarizing the substrate surface.

[0242] Known coating methods can be used. For example, the dropping method, slit coating method, spraying method, roll coating method, spin coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, offset printing, etc. can be mentioned.

[0243] The thickness of the film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 to 20.0 μm, and more preferably 0.3 to 10.0 μm.

[0244] Next, a pattern is formed. Methods for forming a pattern include the photolithography method and the dry etching method, and the photolithography method is preferred. When used as a flat film, the step of forming a pattern may not be performed, and after coating, drying or overall exposure may be performed as needed.

[0245] Hereinafter, the method of forming a pattern by the photolithography method will be described in detail.

[0246] When forming a pattern by the photolithography method, a layer formed by coating the photosensitive composition of the present invention on a substrate is prebaked as needed, then exposed in a pattern through a mask (exposure step), the unexposed portion is removed by alkali development (development step), and then the pattern is heat-treated (post-bake step).

[0247] 〔Exposure step〕 The exposure process involves exposing a layer formed by coating to a specific pattern via a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF-rays (wavelength 248 nm) and ArF-rays (wavelength 193 nm). Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (e.g., at the millisecond level or less) (pulsed exposure).

[0248] [Development process] Next, by treating with an alkaline developer, the unexposed layers dissolve into the alkaline developer, leaving only the hardened parts and resulting in a patterned film. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0249] [Post-baking process] After development, a heat treatment (post-bake) is performed. Post-bake improves the durability of the film. The temperature is preferably between 80 and 300°C. The duration is preferably between 2 minutes and 1 hour. When a material with low heat resistance is used as the substrate, or when a substrate having an organic electroluminescent element as the light-emitting layer is used, the temperature is preferably 150°C or lower, and more preferably 130°C or lower.

[0250] <Color Filter> The film of the present invention can be used in color filters. The color filters of the present invention can be used in solid-state image sensors such as CCDs and CMOS sensors, and image display devices. By appropriately selecting a coloring agent (A), red color filters, green color filters, blue color filters, magenta color filters, cyan color filters, yellow color filters, gray color filters, black color filters, etc., can be obtained. The color filters can be manufactured in the same manner as the film described above.

[0251] <Solid-state image sensor> The solid-state image sensor of the present invention has a film. The form of the solid-state image sensor is not particularly limited, but for example, it has a substrate on which a plurality of photodiodes constituting the light-receiving area of ​​the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like are provided, a light-shielding film is provided on the photodiodes and transfer electrodes with openings only for the light-receiving portion of the photodiodes, a device protective film made of silicon nitride or the like is provided on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiodes, and a filter is provided on the device protective film. Furthermore, it may have a configuration in which a light-gathering means (e.g., a microlens, etc.; the same applies hereinafter) is provided on the device protective film and below the filter (on the side closer to the substrate), or a configuration in which the light-gathering means is provided on the filter. In addition, the filter may have a structure in which the film of the present invention forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. In this case, it is preferable that the partition walls have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), in-vehicle cameras, surveillance cameras, and sensors.

[0252] <Image display device> The image display device of the present invention has a film. Examples of image display devices include liquid crystal displays and organic EL displays. The form used in the image display device is not particularly limited, but it can be used as a color filter or a black matrix. The form used in the image display device is not particularly limited, as long as it functions as an image display device. For example, the configuration described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) is one such example. For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989). [Examples]

[0253] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" refers to "parts by mass" and "%" refers to "percentage by mass". Furthermore, in this invention, non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 230°C for 30 minutes.

[0254] Prior to the examples, each measurement method will be described. The weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows:

[0255] (Average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The average molecular weight is expressed as a polystyrene equivalent.

[0256] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH / g). The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0257] (Amine value of resin) The amine value of the resin is calculated by converting the total amine value (mgKOH / g), which was measured according to the ASTM D 2074 method, into a non-volatile content value.

[0258] <Manufacturing of coloring agent (A1)> (Coloring agent (A1-1)) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85°C. Next, potassium hydroxide aqueous solution was added to adjust the pH to approximately 5, and the mixture was stirred for 90 minutes to prepare the azobarbituric acid precursor. 0.3 moles of azobarbituric acid precursor were mixed with 1,500 parts of distilled water at 82°C, and 10 parts of 30% hydrochloric acid were added dropwise, followed by the addition of 0.6 moles of melamine. Next, 0.195 moles of nickel chloride solution and 0.105 moles of zinc chloride solution were mixed and added dropwise, and the mixture was stirred at 82°C for 3 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5.2, and 100 parts of distilled water were added and the temperature was raised to 90°C. Next, 21 parts of 30% hydrochloric acid were added dropwise and the mixture was stirred for 12 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5, and the product was collected by filtration. The product was washed with deionized water and filtered. After drying at 80°C, it was ground to obtain a coloring agent (A1-1) with a Ni to Zn molar ratio of 65:35. Fifty parts of the obtained coloring agent (A1-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After repeating filtration and washing with deionized water five times, it was dried at 80°C overnight and then pulverized to finely grind the mixture.

[0259] (Coloring agent (A1-2)) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85°C. Next, potassium hydroxide aqueous solution was added to adjust the pH to approximately 5, and the mixture was stirred for 90 minutes to prepare the azobarbituric acid precursor. 0.3 moles of azobarbituric acid precursor were mixed with 1,500 parts of distilled water at 82°C, and 10 parts of 30% hydrochloric acid were added dropwise, followed by the addition of 0.3 moles of melamine. Next, 0.195 moles of nickel chloride solution and 0.105 moles of zinc chloride solution were mixed and added dropwise, and the mixture was stirred at 82°C for 3 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5.2, and 100 parts of distilled water were added and the temperature was raised to 90°C. Next, 21 parts of 30% hydrochloric acid were added dropwise and the mixture was stirred for 12 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5, and the product was collected by filtration. The product was washed with deionized water and filtered. After drying at 80°C, it was ground to obtain a coloring agent (A1-2) with a Ni to Zn molar ratio of 65:35. The obtained colorant (A1-2) was micronized using the same method as colorant (A1-1).

[0260] (Coloring agents (A1-3)) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85°C. Next, potassium hydroxide aqueous solution was added to adjust the pH to approximately 5, and the mixture was stirred for 90 minutes to prepare the azobarbituric acid precursor. 0.3 moles of azobarbituric acid precursor were mixed with 1,500 parts of distilled water at 82°C, and 10 parts of 30% hydrochloric acid were added dropwise, followed by the addition of 0.6 moles of melamine. Next, 0.21 moles of nickel chloride solution and 0.09 moles of copper chloride solution were mixed and added dropwise, and the mixture was stirred at 82°C for 3 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5.2, and 100 parts of distilled water were added and the temperature was raised to 90°C. Next, 21 parts of 30% hydrochloric acid were added dropwise and the mixture was stirred for 12 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5, and the product was collected by filtration. The product was washed with deionized water and filtered. After drying at 80°C, it was ground to obtain a coloring agent (A1-3) with a Ni to Cu molar ratio of 70:30. The obtained colorant (A1-3) was micronized using the same method as colorant (A1-1).

[0261] (Coloring agent (A1-4)) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85°C. Next, potassium hydroxide aqueous solution was added to adjust the pH to approximately 5, and the mixture was stirred for 90 minutes to prepare the azobarbituric acid precursor. 0.3 moles of azobarbituric acid precursor were mixed with 1,500 parts of distilled water at 82°C, and 10 parts of 30% hydrochloric acid were added dropwise, followed by the addition of 0.6 moles of melamine. Next, 0.195 moles of nickel chloride solution, 0.09 moles of zinc chloride solution, and 0.015 moles of copper chloride solution were added dropwise, and the mixture was stirred at 82°C for 3 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5.2, and 100 parts of distilled water were added and the temperature was raised to 90°C. Next, 21 parts of 30% hydrochloric acid were added dropwise and the mixture was stirred for 12 hours. Then, potassium hydroxide was added to adjust the pH to approximately 5, and the product was collected by filtration. The product was washed with deionized water and filtered. After drying at 80°C, it was ground to obtain a coloring agent (A1-4) with a molar ratio of Ni, Zn, and Cu of 65:30:5. The obtained colorant (A1-4) was micronized using the same method as colorant (A1-1).

[0262] <Manufacturing of alkali-soluble resin (B)> (Alkali-soluble resin (B1-1)) 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) were placed in a reaction vessel, which was a separable four-neck flask fitted with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. The vessel was heated to 120°C while nitrogen gas was injected into it. At the same temperature, 49.7 parts of 2-ethylhexyl acrylate (hereinafter referred to as 2-EHA), 99.4 parts of glycidyl methacrylate (hereinafter referred to as GMA), 6.6 parts of dicyclopentanyl methacrylate (hereinafter referred to as DCPMA), 19.0 parts of the polymerization initiator t-butyl peroxy-2-ethylhexanoate, and a mixture of PGMAc were added dropwise over 2.5 hours using a dropping tube. After the dropwise addition was complete, the mixture was stirred at 120°C for a further 2 hours to obtain the precursor. Then, the flask was purged with air, and 50.4 parts of acrylic acid (hereinafter referred to as AA) as the modified compound, along with 0.6 parts of triphenylphosphine and 0.2 parts of methylhydroquinone as catalysts, were added and the mixture was reacted at 110°C for 10 hours. This resulted in the reaction of the epoxy group of GMA with the carboxyl group of AA to obtain monomer units (hereinafter referred to as GMA+AA), which introduced polymerizable unsaturated groups. Next, 21.3 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) were added as a modifying compound, and the mixture was reacted at 110°C for 4 hours. This caused some of the hydroxyl groups of GMA+AA to react with THPA. Subsequently, PGMAc was added to achieve a non-volatile content of 20% by mass, and an alkali-soluble resin (B1-1) was prepared having alicyclic hydrocarbon-containing monomer units (b1), polymerizable unsaturated group-containing monomer units (b2), and monomer units (b3) whose homopolymer glass transition temperature is 0°C or lower. The alkali-soluble resin (B1-1) had an acid value of 38 mgKOH / g and a weight-average molecular weight of 12,000.

[0263] (Alkali-soluble resins (B1-2) to (B1-6)) Alkali-soluble resins (B1-2) to (B1-6) were synthesized using the same method as for alkali-soluble resin (B1-1), by changing the types and amounts of compounds to achieve the composition ratios shown in Table 1. PGMAc was then added to bring the non-volatile content to 20% by mass.

[0264] [Table 1]

[0265] The MAA+GMA shown in Table 1 represents a polymerizable unsaturated monomer unit (b2) obtained by adding the epoxy group of GMA to the carboxyl group of methacrylic acid (hereinafter, MAA) in the precursor. The GMA+AA+SHA represents a polymerizable unsaturated monomer unit (b2) obtained by reacting some of the hydroxyl groups of GMA+AA with succinic anhydride (hereinafter, SHA).

[0266] (Alkali-soluble resin (B2-1)) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 196 parts of cyclohexanone were charged into the vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 25.1 parts benzyl methacrylate, 23.0 parts n-butyl methacrylate, 14.3 parts 2-hydroxyethyl methacrylate, 13.4 parts methacrylic acid, 24.1 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was allowed to continue for another 3 hours. After cooling to room temperature, PGMAc was added to achieve a non-volatile content of 20% by mass to prepare alkali-soluble resin (B2-1). The acid value was 87 mgKOH / g and the weight-average molecular weight was 25,000.

[0267] (Alkali-soluble resins (B2-2) and (B2-3)) Alkali-soluble resins (B2-2) and (B2-3) were synthesized by changing the composition ratios and amounts as shown in Table 2, and PGMAc was added to bring the non-volatile content to 20% by mass.

[0268] [Table 2]

[0269] <Manufacturing of Dispersed Resin (H)> (Dispersion resin containing acidic groups (H1-1)) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc were charged and purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts 2,2'-azobisisobutyronitrile added to 90 parts PGMAc. Non-volatile content measurement confirmed that 95% had reacted. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. After confirming that over 98% of the acid anhydride had undergone half-esterification by measuring the acid value, the reaction was terminated. PGMAc was then added to obtain a dispersion resin (H1-1) containing acidic groups, resulting in a non-volatile content of 30%. The acid value was 70 mgKOH / g, and the weight-average molecular weight was 8,500.

[0270] (Dispersion resin containing acidic groups (H1-2)) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step (on a non-volatile content basis), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the mixture was reacted for 12 hours (second step). Non-volatile content measurement confirmed that 95% had reacted. Finally, 500 parts of a PGMAc diluted solution with 50% non-volatile content of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and IR measurement showed 2270 cm⁻¹ based on the isocyanate group. -1 The reaction was carried out until the peak disappeared (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and PGMAc was added to obtain an acidic dispersion resin (H1-2) with a non-volatile content of 30%. The acid value was 68 mgKOH / g, the unsaturated double bond equivalent was 1,593, and the weight-average molecular weight was 13,000.

[0271] (Dispersion resin containing basic groups (H2-1)) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 30 parts methyl methacrylate, 30 parts n-butyl methacrylate, 20 parts hydroxyethyl methacrylate, and 13.2 parts tetramethylethylenediamine were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate, 5.6 parts cuprous chloride, and 133 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or higher. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-711MM) were added to the reaction apparatus as the monomer for the second block (block A). The reaction was continued by stirring while maintaining a temperature of 110°C and a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added to obtain a dispersion resin (H2-1) having basic groups, with a non-volatile content of 30%. The amine value was 57 mgKOH / g and the number average molecular weight was 4,500 (Mn).

[0272] (Dispersion resin containing basic groups (H2-2)) 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of the initiator dimethylketene methyltrimethylsilyl acetal were added to a 500 mL round-bottom, four-neck separable flask equipped with a condenser, an additive funnel, a nitrogen inlet, a stirrer, and a digital thermometer, via the additive funnel, and the flask was thoroughly purged with nitrogen. 0.5 parts by mass of a 1 mol / L acetonitrile solution of the catalyst tetrabutylammonium m-chlorobenzoate was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate, all solubility-based blocking monomers, were added dropwise over 60 minutes using the additive funnel. The reaction flask was cooled in an ice bath to maintain the temperature below 40°C. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, a monomer for blocking colorant adsorption, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying. Next, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of 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), which is a salt-forming component, was added, and the mixture was stirred at a reaction temperature of 30°C for 20 hours. PGMAc was added to obtain a dispersion resin (H2-2) having basic groups, with a non-volatile content of 30%.

[0273] <Dispersion manufacturing> (Dispersion 1) Using zirconia beads with a diameter of 0.5 mm, dispersion was performed for 3 hours using an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 1.0 μm pore size filter to prepare dispersion 1 with the following composition. The organic solvent (J-1) is PGMAc. Coloring agent (A1-1): 15.0 parts Pigment derivative (G-1): 1.0 part Acidic group-containing dispersion resin (H1-1): 20.0 parts Organic solvent (J-1): 64.0 parts

[0274] Dye derivative (G-1): See below structure [ka]

[0275] Dispersions 2-13 were prepared in the same manner as dispersion 1, except that the raw materials and quantities listed in Table 3 were changed.

[0276] [Table 3]

[0277] The ingredients listed in Table 3 are as follows:

[0278] [Coloring agent (A)] A2-1: Pigment Green 36 A2-2: Pigment Green 58 A2-3: Pigment Green 59 A2-4: Pigment Green 63 A2-5: Pigment Red 254 A2-6: Pigment Red 291 A2-7: Pigment Red 177 A2-8: Pigment Yellow 138 A2-9: Pigment Blue 15:3

[0279] [Dye derivative (G)] [ka]

[0280] <Manufacturing of photosensitive compositions> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive composition 1. Dispersion 1: 10.0 parts Dispersion 6: 30.0 parts Alkali-soluble resin (B1-2): 9.0 parts Alkali-soluble resin (B2-1): 3.0 parts Polymerizable compound (C1-1): 4.0 parts Polymerizable compound (C2-1): 1.2 parts Polymerizable compound (C3-1): 0.5 part Polymerizable compound (C7-1): 0.5 part Polymerization initiator (D1-1): 0.6 parts Polymerization initiator (D2-1): 0.6 parts Thermosetting compound (E1-1): 0.3 part Sensitizer (F-1): 0.3 parts Leveling agent (I): 1.0 part Organic solvent (J): 39.0 parts

[0281] [Examples 2-37, Comparative Example 1] (Photosensitive composition 2-38) Photosensitive compositions 2 to 38 were prepared in the same manner as in Example 1, except that the raw materials and quantities of photosensitive composition 1 in Example 1 were changed to those listed in Tables 4-1 to 4-4.

[0282] [Table 4-1]

[0283] [Table 4-2]

[0284] [Table 4-3]

[0285] [Table 4-4]

[0286] The ingredients listed in Tables 4-1 to 4-4 are as follows:

[0287] [Polymerizable compound (C)] (Lactone-modified polymerizable compound (C1)) C1-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.) C1-2: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)

[0288] (Polymerizable compound (C2) containing an acidic group) C2-1: Arronix M-520 (manufactured by Toagosei Co., Ltd.)

[0289] (Molybdenum-containing polymerizable compound (C3)) C3-1: Dipentaerythritol pentaacrylate

[0290] (Other polymerizable compounds (C7)) C7-1: Dipentaerythritol hexaacrylate

[0291] [Polymerization initiator (D)] (Oxime in one molecule) ester Polymerization initiator having two groups (D1) D1-1: Compound (D1-1) as described above. D1-4: Compounds (D1-4) described above. D1-6: Compounds (D1-6) described above.

[0292] (Other polymerization initiators (D2)) D2-1: The following compounds [ka]

[0293] D2-2: Omnirad 369 (manufactured by IGM Resins) D2-3: Omnirad 907 (manufactured by IGM Resins) D2-4: IRGACURE OXE01 (manufactured by BASF Japan)

[0294] [Thermosetting compound (H)] (Epoxy compound (E1)) E1-1: EHPE-3150 (manufactured by Daicel Corporation, compound represented by general formula (7), with approximately 15 epoxy groups, epoxy equivalent weight of 170-190 g / eq) E1-2: EPICLON N-770 (manufactured by DIC, an epoxy compound with aromatic rings, 8 epoxy groups, epoxy equivalent weight 180-200 g / eq)

[0295] [Sensitizer (F)] F-1: 2,4-Diethylthioxanthone

[0296] [Leveling agent (I)] I-1: BYK-330 (manufactured by BYK Chemie) I-2: Megafuck F-551 (manufactured by DIC Corporation) As described above, (I-1) and (I-2) were mixed in 1 part each and dissolved in 98 parts of PGMAc to form a mixed solution which was used as leveling agent (I).

[0297] [Organic solvents (J)] J-1: Propylene glycol monomethyl ether acetate 30 parts J-2: Cyclohexanone 30 parts J-3: 3-Ethoxypropionate 10 parts J-4: Propylene glycol monomethyl ether 10 parts J-5: Cyclohexanol acetate 10 parts J-6: Dipropylene glycol methyl ether acetate 10 parts The above (J-1) to (J-6) were mixed in the above-mentioned parts by mass to obtain organic solvent (J).

[0298] <Evaluation of photosensitive compositions> The line width, cross-sectional shape, residual film percentage, and solvent resistance of the obtained photosensitive compositions 1 to 38 (Examples 1 to 37, Comparative Example 1) were evaluated using the following methods. The evaluation results are shown in Table 5.

[0299] [Line width] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, after the substrate was cooled to room temperature, it was exposed to ultraviolet light using a high-pressure mercury lamp through a photomask with a 25 μm wide stripe pattern. The exposure amount was adjusted so that the average width of 50 lines in the pattern obtained after development was 25 μm. Subsequently, the substrate was spray developed at 23°C using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide, washed with deionized water, and air-dried. The obtained substrate was subjected to a Nikon ECLIPSE LV100POL Model optical microscope, and the line width of 50 patterns was measured to determine the line width variation (3σ). The evaluation criteria were as follows, with a value of 3 or higher indicating practical usability. 5: Line width variation is less than 1.0 μm. 4: Line width variation is 1.0 μm or more and less than 1.5 μm. 3: Line width variation is 1.5 μm or more and less than 3.0 μm. 2: Line width variation is 3.0 μm or more and less than 3.5 μm. 1: Line width variation of 3.5 μm or more

[0300] [Cross-sectional shape] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. After cooling the substrate to room temperature, it was illuminated at 30 mW / cm² using a high-pressure mercury lamp through a 100 μm wide stripe pattern photomask. 2 50 mJ / cm² 2The substrate was exposed to light. Subsequently, the substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C. After that, it was washed with deionized water, air-dried, and heated in a clean oven at 230°C for 30 minutes. Spray development was performed for the shortest possible time that allowed for pattern formation without any development residue for each photosensitive composition. The cross-sectional shape of the pattern was confirmed using a scanning electron microscope (Hitachi High-Tech Corporation's "S-3000H"). The evaluation involved acquiring SEM images of the cross-section of a 100 μm wide stripe pattern and measuring the taper angle between the substrate and the edge of the pattern cross-section. The evaluation criteria were as follows, with a score of 3 or higher indicating practical usability. 5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle 50 degrees or more and less than 60 degrees 3: Taper angle of 30 degrees or more but less than 40 degrees, or 60 degrees or more but less than 70 degrees 2: Taper angle of 20 degrees or more but less than 30 degrees, or 70 degrees or more but less than 90 degrees 1: Taper angle less than 20 degrees, or 90 degrees or more.

[0301] [Percentage of remaining film] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. After cooling the substrate to room temperature, it was illuminated at 30 mW / cm² using a high-pressure mercury lamp through a 100 μm wide stripe pattern photomask. 2 50 mJ / cm² 2 The substrate was exposed to light. Subsequently, the substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C. The film thickness of the coating was measured after washing with deionized water and air-drying. This film thickness was defined as the post-development film thickness. Spray development was performed for the shortest possible time that allowed for pattern formation without any development residue for each photosensitive composition. Subsequently, the film was heated in a clean oven at 230°C for 30 minutes, and the film thickness was measured again at the same location where the film thickness after development had been measured. This film thickness was defined as the post-bake film thickness. The residual film percentage was calculated from the two film thicknesses using the following formula. A percentage of 3 or higher is considered practical. The film thickness was measured using a Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.). Formula: Residual film percentage (%) = Film thickness after baking ÷ Film thickness after development × 100 5: Remaining film rate 85% or more 4: Residual film rate 80% or more but less than 85% 3: Residual film rate 75% or more but less than 80% 2: Residual film rate 70% or more but less than 75% 1: Residual film rate less than 70%

[0302] [Solvent resistance] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. After cooling the substrate to room temperature, illuminating it with a high-pressure mercury lamp at 30 mW / cm² through a 100 μm wide stripe pattern photomask. 2 50 mJ / cm² 2 The substrate was exposed to light. After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with deionized water, and air-dried. The resulting substrate was heated in a clean oven at 230°C for 30 minutes to obtain an evaluation substrate. Spray development was performed for the shortest possible time that allowed for pattern formation without any development residue for each photosensitive composition. The obtained evaluation substrates were immersed in N-methylpyrrolidone at room temperature for 15 minutes, washed with deionized water, air-dried, and observed using an optical microscope on the 100 μm wide stripe pattern area. The evaluation criteria are as follows, with a score of 3 or higher indicating practical usability. 5: There is no change in appearance or color. 4: Slight wrinkles may appear, but there is no change in color. 3: Some wrinkles may appear, but there is no change in color. 2: Wrinkles and other marks may appear throughout, and the color may fade slightly. 1: Peeling and fading may occur.

[0303] [Table 5]

Claims

1. A photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), The coloring agent (A) includes a coloring agent (A1) comprising at least two different metal azo compounds selected from the group consisting of a metal azo compound represented by the following general formula (1) and a metal azo compound having a tautomer structure thereof, and a compound represented by the following general formula (2). The alkali-soluble resin (B) is an alicyclic hydrocarbon-containing monomer unit (b1), and polymerized It contains an alkali-soluble resin (B1) having an alkali-unsaturated group-containing monomer unit (b2), A photosensitive composition wherein the polymerization initiator (D) comprises a polymerization initiator (D1) having two oxime ester groups in one molecule. General formula (1) 【Chemistry 1】 (In general formula (1), R １ and R ２ These are OH and NH, respectively, independently. ２ , or NHR ５ To represent And, R ３ and R ４ These are independently =O or =NR ５ Represents R ５ is a hydrogen atom, Alternatively, it represents an alkyl group which may have substituents. Me is Ni, Zn, Cu, Al, Fe, (It is a metal ion selected from the group consisting of Co and Mn.) General formula (2) 【Chemistry 2】 (In general formula (2), the three Rs ６ each independently may have a hydrogen atom or a substituent (Represents an alkyl group.)

2. The photosensitive composition according to claim 1, wherein the polymerization initiator (D1) having two oxime ester groups in one molecule comprises a compound represented by the following general formula (3). General formula (3) 【Transformation 3】 (In general formula (3), X １ and X ２ Each of these independently represents -CO- or a single bond. ３ R represents a single bond or a sulfur atom. １ R represents an alkyl group having 1 to 20 carbon atoms. ２ and R ３ Each of these is independently a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, and an alkyl group with 2 to 30 carbon atoms. The heterocycle, the aryl group having 6 to 30 carbon atoms, or the arylalkyl group having 7 to 30 carbon atoms are represented. R ４ and R ５ These are, independently, alkyl groups with 1 to 20 carbon atoms and alkyl groups with 2 to 30 carbon atoms. Heterocyclic groups, aryl groups with 6 to 30 carbon atoms, or arylalkyl groups with 7 to 30 carbon atoms are represented. Yes. Two R ６ (Each of these independently represents either a hydrogen atom or a nitro group.)

3. Furthermore, the photosensitive composition according to claim 1, further comprising a thermosetting compound (E).

4. A film comprising the photosensitive composition according to any one of claims 1 to 3.

5. A color filter having the film described in claim 4.

6. A solid-state image sensor having the film described in claim 4.

7. An image display device having the film described in claim 4.

Images