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

Abstract

This invention satisfies the requirements of adhesion, rectangular dimensions, adhesion, and developability of unexposed areas. [Solution] A photosensitive composition comprising a colorant (A), an oxime ester-based photopolymerization initiator (B), a polymerizable compound (C), and a resin (D), The content of the coloring agent (A) is 50% by mass or more and 70% by mass or less of the total solid content of the photosensitive composition by 100% by mass. The polymerizable compound (C) has an alkylene oxide modified unit and an ethylenically unsaturated double bond group, A photosensitive composition characterized in that the resin (D) comprises a resin (D1) having a urethane bond and an ethylenically unsaturated double bond group and a molecular weight of 10,000 or more and 30,000 or less.

Description

Technical Field

[0001] The present invention relates to an optical filter, an image display device, a solid-state imaging device, and a photosensitive composition used for forming the same.

Background Art

[0002] An optical filter is formed by arranging two or more kinds of fine strip-shaped filter segments having different hues parallel to each other (in a stripe shape) or intersecting on a transparent substrate such as a glass substrate, or by arranging two or more kinds of fine filter segments having different hues in order in each of the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundred microns and are neatly arranged in a predetermined arrangement for each hue. Currently, as a method for manufacturing an optical filter, a method called a pigment dispersion method that uses a pigment excellent in various resistances such as light resistance and heat resistance as a coloring material is the mainstream. In the pigment dispersion method, an optical filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from this coating film by drying, this coating film is exposed with a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of this coating film is removed by development, and then, if necessary, a treatment such as heating is performed. Thereby, a filter segment pattern of the first color is obtained. Then, by performing the same operation as this, filter segment patterns of other colors are formed to complete an optical filter.

[0003] In recent years, improvement of high color reproducibility of displays has become an important trend. The improvement of high color reproducibility of displays has been mainly studied by enhancing the color reproducibility of the backlight, but it is necessary to use very dark colors in order to improve the color reproducibility of color filters as well. In such a case, in the exposure process for forming the pattern of the optical filter, since the amount of light reaching the bottom of the coating film becomes weak, photo-curing tends to be insufficient, and a problem occurs that a pattern of a desired shape cannot be obtained.

[0004] Specifically, photosensitive colored compositions are required to have dimensional stability such that the dimensions of the pattern obtained in the optical filter manufacturing process remain within a certain range even when the exposure amount in the exposure process is varied. However, photosensitive colored compositions that achieve high color reproduction tend to have poorer dimensional stability. Similarly, photosensitive colored compositions that achieve high color reproduction tend to have poorer linearity of the pattern.

[0005] Various methods have been considered to solve these problems. For example, patent documents In References 1 and 2, the pattern shape is improved by adding polymers or compounds with specific structures to the photosensitive composition. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2009-63767 [Patent Document 2] Patent No. 5105867 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] This invention has been made in view of the above circumstances, and aims to provide a photosensitive composition and an optical filter manufactured from such a photosensitive composition that achieves at an even higher level the adhesion, rectangular dimensions, and developability of unexposed areas required for a photosensitive colored composition, even under high colorant content. [Means for solving the problem]

[0008] The present invention relates to a photosensitive composition comprising a colorant (A), an oxime ester-based photopolymerization initiator (B), a polymerizable compound (C), and a resin (D), The content of the coloring agent (A) is 50% by mass or more and 70% by mass or less of the total solid content of the photosensitive composition by 100% by mass. The polymerizable compound (C) has an alkylene oxide modified unit and an ethylenically unsaturated double bond group, The present invention relates to a photosensitive composition characterized in that the resin (D) comprises a resin (D1) having a urethane bond and an ethylenically unsaturated double bond group and a molecular weight of 10,000 or more and 30,000 or less.

[0009] In other words, the present invention relates to the photosensitive composition characterized by containing a polymerizable compound (C1) having three or fewer ethylenically unsaturated double bond groups.

[0010] In other words, the present invention relates to the photosensitive composition characterized in that resin (D) further comprises resin (D2) (excluding resin (D1)) having an acid value of 100 mg KOH / g or more and 150 mg KOH / g or less.

[0011] In other words, the present invention relates to the photosensitive composition characterized in that the total solid content of a resin (D1) having urethane bonds and ethylenically unsaturated double bond groups and a molecular weight of 10,000 to 30,000, and a resin (D2) having an acid value of 100 mg KOH / g to 150 mg KOH / g, is 80% to 99% by mass of the total solid content of resin (D) by 100% by mass.

[0012] In other words, the present invention relates to an optical filter manufactured using the photosensitive composition.

[0013] In other words, the present invention relates to a display element using the optical filter.

[0014] In other words, the present invention relates to a solid-state image sensor using the optical filter described above. [Effects of the Invention]

[0015] According to the present invention described above, it is possible to provide a photosensitive composition that exhibits excellent adhesion of the formed pattern, rectangularity of dimensions, developability of unexposed areas, and chemical resistance, even at high pigment concentrations. Furthermore, the present invention can provide optical filters, image display devices, and solid-state image sensors.

Brief Description of Drawings

[0016] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device.

Embodiments for Carrying Out the Invention

[0017] Hereinafter, each constituent of the photosensitive composition of the present invention will be described. In the present application, when expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, they respectively represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "C.I." mentioned in this specification means Color Index (C.I.). The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, a (meth)acryloyl group, a (meth)allyl group, etc.

[0018] The photosensitive composition of the present invention is a photosensitive composition containing a colorant (A), an oxime ester-based photopolymerization initiator (B), a polymerizable compound (C), and a resin (D), wherein the content of the colorant (A) is 50% by mass or more and 70% by mass or less in 100% by mass of the total solid content of the photosensitive composition, the polymerizable compound (C) has an alkylene oxide-modified unit and an ethylenically unsaturated double bond group, and the resin (D) contains a resin (D1) having a urethane bond and an ethylenically unsaturated double bond group and having a molecular weight of 10,000 or more and 30,000 or less. The photosensitive composition of the present invention is used by forming a film. The film is preferably used for an optical filter.

[0019] By including a polymerizable compound (C) having an alkylene oxide modification unit and an ethylenically unsaturated double bond group, the film formed from the photosensitive composition of the present invention is considered to have high developability in the unexposed portion due to the flexibility of the alkylene oxide modification unit. Further, by including a resin (D1) having a urethane bond and an ethylenically unsaturated double bond group and having a molecular weight of 10,000 or more and 30,000 or less, the film formed from the photosensitive composition of the present invention is considered to be excellent in adhesion and dimensional rectangularity due to improved curability.

[0020] <Colorant (A)> In the photosensitive composition of the present invention, examples of the colorant (A) include pigments, dyes, and near-infrared absorbing colorants. Examples of the pigments include inorganic pigments and organic pigments. 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. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are particularly preferred.

[0021] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0022] 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, and the pigments described in JP 2012-226110. Among these, the pigments described in CI Pigment Yellow 138, 139, 150, 185, 231, 233 and Japanese Patent Publication No. 2012-226110 are preferred.

[0023] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 7, 36, 58, 59, 62, and 63 are preferred.

[0024] 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, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 16 are preferred.

[0025] 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. Among these, CI Pigment Violet 19 and 23 are preferred.

[0026] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0027] Furthermore, examples of inorganic pigments include 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.

[0028] The coloring agent (A) can be used alone or in combination of two or more types.

[0029] The total content of colorant (A) is preferably 50 to 70% by mass, and more preferably 50 to 65% by mass, of the total solids content of the photosensitive composition. If the content of colorant (A) exceeds 70% by mass, the content of polymerizable compound (C) becomes low, which adversely affects curability and deteriorates adhesion.

[0030] (Fine-graining of organic pigments) Organic pigments are preferably used after being 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.

[0031] 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 the above organic solvent. The amount of resin added is preferably 2 to 200% by mass relative to 100% by mass of the pigment.

[0032] <Oxime ester-based photopolymerization initiator (B)> Oxime ester-based photopolymerization initiator (B) undergoes cleavage of the NO bond in the oxime upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly reactive radicals, resulting in improved photocurability as patterns can be formed with less exposure compared to using other photopolymerization initiators.

[0033] Oxime ester-based photopolymerization initiators (B) can be classified by their molecular skeleton into carbazole skeletons, fluorene skeletons, diphenyl skeletons, and dioxime-based initiators having two oxime ester groups. Furthermore, preferred specific molecular structures include hydroxyl groups, nitro groups, carbonyl groups, fluorinated carbon groups, and benzofurans.

[0034] Among these, oxime ester photopolymerization initiators having a carbazole structure, oxime ester photopolymerization initiators having a diphenyl skeleton, and oxime ester photopolymerization initiators having two oxime ester groups (including those having a carbazole skeleton) are preferred, with oxime ester photopolymerization initiators having a carbazole structure being the most preferred. Furthermore, for oxime ester photopolymerization initiators having a diphenyl skeleton, if the molecular weight of the radical compound generated during exposure is high, the mobility within the coating film decreases and the radical reactivity with polymerizable compounds decreases. Therefore, it is preferable that the terminal end of the ester group in the oxime ester group does not become a phenyl ester.

[0035] Other oxime ester-based photopolymerization initiators include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

[0036] Examples of oxime ester-based photopolymerization initiators include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Compounds described in Technology (1995, pp. 202-232), compounds described in JP 2000-66385, compounds described in JP 2000-80068, compounds described in JP 2004-534797, compounds described in JP 2006-342166, compounds described in JP 2017-19766, compounds described in Japanese Patent No. 6065596, International Publication Examples include compounds described in WO2015 / 152153, compounds described in International Publication WO2017 / 051680, compounds described in JP 2007-210991, compounds described in JP 2009-179619, compounds described in JP 2010-037223, compounds described in JP 2010-215575, and compounds described in JP 2011-020998. Commercially available products include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03, Irgacure OXE-04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). Furthermore, it is preferable to use compounds that do not produce color or compounds that are highly transparent and resistant to discoloration as oxime compounds. Commercially available products include Adeka Cruise NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

[0037] In the present invention, the oxime ester-based photopolymerization initiator (B) is preferably present in an amount of 0.5 to 5% by mass of 100% by mass of the total solids content of the photosensitive composition. When within this range, the photocurability is excellent and the adhesion is improved.

[0038] <Polymerizable compound (C)> The polymerizable compound (C) in the present invention is a monomer or oligomer that hardens upon exposure to ultraviolet light or heat to produce a transparent resin, and the photosensitive composition of the present invention is characterized by containing a polymerizable compound (C) having an alkylene oxide-modified unit and an ethylenically unsaturated double bond group. The polymerizable compound (C) having alkylene oxide-modified units improves the flexibility of its molecular chains, contributing to improved developability of the unexposed areas of the film made from the photosensitive composition of the present invention. The number of alkylene oxide-modified units contained in the polymerizable compound (C) is preferably 1 to 15 per ethylenically unsaturated bond group, which further enhances the above tendency.

[0039] The content of polymerizable compound (C) is preferably 5 to 15% by mass of 100% by mass of the total solids content of the photosensitive composition, from the viewpoint of having the curability necessary to form the rectangular shape of the pixels. If the content of polymerizable compound (C) is less than 5% by mass of 100% by mass of the total solids content, the curability will be insufficient and will affect the rectangular shape of the pixels.

[0040] As commercially available polymerizable compounds (C) having an alkylene oxide-modified unit and an ethylenically unsaturated double bond group, suitable candidates include KAYARAD DPEA-12 from Nippon Kayaku Co., Ltd., and M-460, M-310, M-321, M-350, M-360, M-920, M-930 from Toagosei Co., Ltd., and NK ester ABE-300, A-GLY-3E, A-GLY-6E, A-GLY-9E from Shin Nakamura Chemical Co., Ltd.

[0041] In the present invention, the polymerizable compound (C) preferably includes polymerizable compound (C1) having three or fewer ethylenically unsaturated double bond groups. When there are three or fewer ethylenically unsaturated double bond groups, the molecular weight of polymerizable compound (C) decreases, and the development residue in the unexposed areas becomes even better.

[0042] Examples of commercially available polymerizable compounds (C1) with three or fewer ethylenically unsaturated double bond groups include Aronics M-310, M-321, M-350, and M-360 from Toagosei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Examples include NK ester ABE-300, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-3P, A-GLY-6P, and A-GLY-9P, all manufactured by Shin-Nakamura Chemical Co., Ltd.

[0043] <Resin (D)> The photosensitive composition of this embodiment contains a resin (D), wherein the resin (D) contains a resin (D1) having a urethane bond and an ethylenically unsaturated double bond group and a molecular weight of 10,000 to 30,000. From the viewpoint of the spectral characteristics of the pixels, the resin (D) is preferably a resin with a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region. In addition to the resins (D1) and (D2) described later, other resins such as thermoplastic resins, thermoplastic resins, photosensitive resins, and pigment dispersion resins can be used as resin (D) individually or in combination of two or more. From the viewpoint of adhesion and pattern shape, the content of resin (D) is preferably 0.5 to 25% by mass, and more preferably 5 to 25% by mass, of the total solid content of the photosensitive composition.

[0044] The photosensitive composition of the present invention includes a resin (D1) as the resin (D), which has urethane bonds and ethylenically unsaturated double bond groups and a molecular weight of 10,000 or more and 30,000 or less. By forming crosslinks through photocuring of the ethylenically unsaturated double bond groups and hydrogen bonding of the urethane bonds, the curability of the photosensitive composition of the present invention is improved, resulting in good adhesion and rectangular dimensions. The molecular weight of the resin (D1) is preferably 10,000 or more from the viewpoint of the rectangular pixels of the film made from the photosensitive composition of the present invention, and preferably 30,000 or less from the viewpoint of developability. In particular, the molecular weight of the resin (D1) is more preferably 10,000 or more and 20,000 or less. If the molecular weight is less than 10,000, adhesion deteriorates due to curing shrinkage of the photocured portion. If the molecular weight is greater than 30,000, it adversely affects the residue after development of the unexposed portion. The content of the resin (D1) is preferably 3% by mass or more and 30% by mass or less in 100% by mass of the total solids content of the photosensitive composition.

[0045] One method for obtaining a resin (D1) having urethane bonds and ethylenically unsaturated double bond groups, and having a molecular weight of 10,000 or more and 30,000 or less, involves using an ethylenically unsaturated monomer having a hydroxyl group and reacting the side-chain hydroxyl group of a copolymer obtained by copolymerizing it with another unsaturated monobasic acid monomer having a carboxyl group, or with another monomer, with the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group. Examples of ethylenically unsaturated monomers having a hydroxyl group include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. These may be used individually or in combination of two or more types.

[0046] Examples of ethylenically unsaturated monomers having an isocyanate group include, but are not limited to, 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate. The ethylenically unsaturated monomer having an isocyanate group may be used alone or You can use two or more types together.

[0047] Furthermore, it is preferable that resin (D) further contains resin (D2) (excluding resin (D1)) having an acid value of 100 mg KOH / g to 150 mg KOH / g. Including resin (D2) significantly improves the developability of the unexposed portion of the film made from the photosensitive composition of the present invention. The acid value of resin (D2) is preferably 100 mg KOH / g or more to resolve the issue of developability of the unexposed portion of the film, preferably 150 mg KOH / g or less from the viewpoint of adhesion, and more preferably 100 mg KOH / g to 120 mg KOH / g from the viewpoint of balancing developability and adhesion of the unexposed portion.

[0048] Examples of monomers that make up resin (D2) with an acid value of 100 mg KOH / g to 150 mg KOH / g include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2- (Meth)acrylates such as ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N (meth)acrylamides such as N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl fatty acid compounds such as vinyl acetate or vinyl propionate, etc.

[0049] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3- N-substituted maleimides such as maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimide acridine, as well as resin (D), can be used alone or in combination of two or more types. The content of resin (D2), which has a KOH content of 100 mg to 150 mg, is preferably 1% to 25% by mass of the total solid content of the photosensitive composition (100% by mass).

[0050] Preferably, the total content of resin (D1), which has urethane bonds and ethylenically unsaturated double bond groups and a molecular weight of 10,000 to 30,000, and resin (D2), which has an acid value of 100 mg KOH / g to 150 mg KOH / g, is 80% to 99% by mass of the total solid content of resin (D) by 100% by mass.

[0051] Examples of thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cycloadhesive rubber resin, cellulose, polyethylene, polybutadiene, and polyimide resin.

[0052] As photosensitive resins, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymers and α-olefin-maleic anhydride copolymers are also used, which are half-esterified with (meth)acrylic compounds having hydroxyl groups, such as hydroxyalkyl (meth)acrylates.

[0053] The photosensitive resin preferably has ethylenically unsaturated double bond groups. By using a resin other than resin (D1) that has ethylenically unsaturated double bond groups introduced into it, the resin undergoes three-dimensional crosslinking when exposed to active energy rays to form a coating film, increasing the crosslinking density and improving chemical resistance.

[0054] For example, one method involves copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers to obtain a copolymer, then adding the carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond group to the side-chain epoxy group of the copolymer, and further reacting the resulting hydroxyl group with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond group and a carboxyl group.

[0055] Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used individually or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

[0056] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid. These may be used individually or in combination of two or more types.

[0057] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, which may be used individually or in combination of two or more. If necessary, such as to increase the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. Furthermore, by using tetrahydrophthalic anhydride or maleic anhydride, which have ethylenically unsaturated double bond groups, as the polybasic acid anhydride, the number of ethylenically unsaturated double bond groups can be further increased.

[0058] A similar method involves copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers to obtain a copolymer, and then adding an ethylenically unsaturated monomer having an epoxy group to some of the side-chain carboxyl groups of the copolymer to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0059] [Polymerization inhibitor (F)] The photosensitive composition of the present invention may contain a polymerization inhibitor (F). The photosensitive composition of the present invention may contain a polymerization inhibitor to prevent photosensitivity due to diffracted light from the mask during exposure. Adding a polymerization inhibitor provides the effect of preventing curing from progressing beyond the desired pattern through photosensitive chain polymerization.

[0060] Polymerization inhibitors include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butyl Examples include alkylresorcinol compounds such as resorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and trimenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0061] Polymerization inhibitor (F) is an organic compound having ultraviolet light absorption function, and examples include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylate organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds.

[0062] The polymerization inhibitor (F) content is preferably 0.01 to 1% by mass of 100% by mass of the total solids content of the photosensitive composition.

[0063] [Leveling agent (L)] The photosensitive composition of the present invention may contain a leveling agent (L). This further improves the wettability and drying properties to the substrate during coating. Examples of leveling agents (L) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0064] Silicone-based surfactants include, for example, linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0065] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Bic Chemie, and FZ-7002, 211 from Toray Dow Corning. Examples include 0, 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.

[0066] Examples of fluorinated surfactants include surfactants or leveling agents having fluorocarbon chains.

[0067] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical; 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; FC-4430 and 4432 from Sumitomo 3M; EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals; and Futergent 602A from Neos.

[0068] 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.

[0069] Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, L S-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-L120, TW -L106,TW-P120,TW-S120V,TW-S320V,TW-O120V,TW-O106V,TW-IS399C, Super TW-L120,430V,440V,460V,MS-50,MS-60,MO-60,MS-165V, Emanon 1112,3199V,3299V,3299RV,4110,CH-25,CH-40,CH-60(K), Ami-to 102 Examples include 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 copolymer Polyflow-No.75, No.90, No.95.

[0070] 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.

[0071] Examples of commercially available products include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate, all manufactured by Kao Corporation.

[0072] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, 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 styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0073] Examples of commercially available products include Neos's Futergent 100 and 150, and ADEKA's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, and EC-8600.

[0074] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0075] Examples of commercially available products include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N, manufactured by Kao Corporation.

[0076] Leveling agent (L) can be used alone or in combination of two or more types.

[0077] The leveling agent (L) content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the total solids content of the photosensitive composition. Within this range, the balance between the applicability and adhesion of the photosensitive composition is further improved. [Colorant derivative (N)] The photosensitive composition of the present invention may contain a colorant derivative (N).

[0078] Colorant derivatives (N) are dispersing aids and include, for example, compounds having a structure in which part of the colorant is substituted with an acidic group, a basic group, a neutral group, etc. Colorant derivatives (N) include, for example, 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 the colorants include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiaidine indigo compounds, triazine compounds, benzimidazolon compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, surene compounds, naphthalocyanine compounds, and the like.

[0079] Specifically, as pyrrolopyrrole-based colorant derivatives, see Japanese Patent Publication No. 2001-220520, International Publication No. 2009 / 081930, International Publication No. 2011 / 052617, International Publication No. 2012 / 102399, Japanese Patent Publication No. 2017-156397, International Publication No. 2018 / 101189; as phthalocyanine-based colorant derivatives, see Japanese Patent Publication No. 2007-226161, International Publication No. 2016 / 163351, Japanese Patent Publication No. 2017-165820, Japanese Patent No. 5753266; as anthraquinone-based colorant derivatives, see Japanese Patent Publication No. 63-2 Japanese Patent Publication No. 64674, 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 colorant derivatives, Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, as dioxazine-based colorant derivatives, Japanese Patent Publication No. 2011-162662, as thiaidine indigo-based colorant derivatives, Japanese Patent Publication No. 2007-314785, as triazine-based colorant derivatives As for JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, as for benzoisoindole-based coloring agent derivatives, JP-A-2009-57478, as for quinophthalone-based coloring agent derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, as for naphthol-based coloring agent derivatives, Examples of known colorant derivatives include those described in Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439, as well as International Publication No. 2020 / 054718 for squarylium-based colorant derivatives, as well as those described in Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092 for azo-based colorant derivatives, as well as those described in Japanese Patent Publication No. 2004-307854 for acidic substituents, and those described in 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 for basic substituents.Note that these documents may refer to them as derivatives, pigment derivatives, dispersants, dispersing aids, pigment dispersants, or simply compounds, but these are synonymous with colorant derivatives (N).

[0080] The colorant derivative (N) can be used alone or in combination of two or more types.

[0081] [Polymerizable compounds (M) that do not contain alkylene oxide-modified units] The photosensitive composition of the present invention may contain a polymerizable compound (M) that does not contain an alkylene oxide-modified unit.

[0082] Examples of commercially available polymerizable compounds (M) that do not contain alkylene oxide-modified units include Aronics M-400, M-402, M-403, M-404, M-405, and M-406 manufactured by Toagosei Co., Ltd.

[0083] Polymerizable compounds (M) that do not contain alkylene oxide-modified units can be used alone or in combination of two or more types.

[0084] [Organic solvent (O)] The photosensitive composition of the present invention may contain an organic solvent (O).

[0085] Organic solvents (O) include, 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-Methylbutylacetate, 3-Methoxybutanol, 3-Methoxybutylacetate, 4-Heptanone, m-Xylene, m-Diethylbenzene, m-Dichlorobenzene, N,N-Dimethylacetamide, N,N-Dimethylformamide, n-Butyl alcohol, n-Butylbenzene, n-Propylacetate, N-Methylpyrrolidone, o-Xylene, o-Chloritolene, o-Diethylbenzene, o-Dichlorobenzene, p-Chloritolene, p-Diethylbenzene, sec-Butylbenzene, tert-Butylbenzene, γ-Butyl Lactone, 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,Examples include dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, and the like. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0086] Organic solvents (O) can be used alone or in combination of two or more types. The content of the organic solvent (O) is preferably 60 to 90% by mass of 100% by mass of the photosensitive composition.

[0087] [Method for producing a photosensitive composition] The photosensitive composition of the present invention can be produced by, for example, adding a colorant (A), a resin (D), an organic solvent (O), etc., and performing a dispersion treatment to produce a dispersion. Subsequently, a polymerizable compound (C) and a resin (D) are blended and mixed into the dispersion. The timing of blending each material is arbitrary. Furthermore, the dispersion process can be performed multiple times.

[0088] Distributed processing machines include, for example, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0089] 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.

[0090] The method for measuring the average dispersed particle diameter (secondary particle diameter) is, for example, to use Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power-spectrum method), with particle permeability set to absorption mode and particle shape set to non-spherical, and the D50 particle diameter defined as the average dispersed particle diameter. The diluent solvent for measurement is the same organic solvent used for dispersion, and it is preferable to measure immediately after sample preparation of the ultrasonically treated sample to obtain results with less variation.

[0091] The photosensitive composition of the present invention is preferably subjected to filtration by means of centrifugal separation, sintered filters, or membrane filters to remove coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, more preferably coarse particles of 0.5 μm or larger, and any mixed dust. The photosensitive composition of the present invention is preferably substantially free of particles of 0.5 μm or larger, and more preferably free of particles of 0.3 μm or smaller.

[0092] <Optical filters> The optical filter of the present invention comprises a substrate and a coating formed from the photosensitive composition of the present invention. The coating can be used as various optical filters by appropriately selecting the type of colorant (A) to be used. For example, red, green, and blue filter segments for optical filter applications can be formed using organic pigments. Alternatively, magenta, cyan, and yellow filter segments can be formed. Furthermore, near-infrared absorbing colorants can be used to form near-infrared transmitting filters or near-infrared cutting filters.

[0093] Examples of substrates include transparent substrates and reflective substrates. Transparent substrates include, for example, glass substrates. Reflective substrates include, for example, substrates that use aluminum electrodes or thin metal films as reflective surfaces.

[0094] [Method for manufacturing optical filters] The method for manufacturing an optical filter is not limited, but photolithography is preferred. For example, it can be manufactured by a step of applying a photosensitive composition to a substrate to form a film (1), exposing the film to light in a patterned manner through a mask (2), alkaline developing the unexposed areas to form a patterned cured film (3), and heat-treating the pattern (post-bake) (4).

[0095] The manufacturing method of optical filters will be described in detail below. (Process (1)) The film formation step (1) involves applying the photosensitive composition onto the substrate by methods such as rotary coating, roll coating, slit coating, casting coating, or inkjet coating, and then drying (pre-baking) it for about 10 to 120 seconds at a temperature of about 50 to 120°C using an oven, hot plate, etc., if necessary. Examples of the substrate include glass substrates and silicon substrates. For example, an image sensor such as a CCD or CMOS may be formed on the surface of the silicon substrate. In addition, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface. The film thickness is preferably 0.05 to 10.0 μm dry, and more preferably 0.3 to 5 μm.

[0096] (Process (2)) In the exposure process, the film obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. This results in a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

[0097] (Step (3)) The cured film obtained in step (2) is subjected to alkaline development treatment, which causes the unexposed portions of the film to dissolve in the alkaline aqueous solution, leaving only the cured portions and resulting in a patterned cured film. Examples of developing solutions 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, pyrrol, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The developer concentration 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 11-13, and more preferably 11.5-12.5. Using a suitable pH suppresses pattern roughness and peeling, and improves the residual film rate after development.

[0098] 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.

[0099] (Step (4)) The heat treatment (post-bake) is used to fully harden the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 100 to 300°C, and more preferably 150 to 250°C. The heating time is preferably 2 minutes to 1 hour, and more preferably 3 minutes to 30 minutes.

[0100] <Image display device> The image display device of the present invention includes an optical filter. 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).

[0101] <Solid-state image sensor> The solid-state image sensor of the present invention includes an optical filter. The form used for the solid-state image sensor is not particularly limited, but for example, it may have 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 with an opening only for the light-receiving portion of the photodiode is provided on the photodiode and transfer electrodes, 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 photodiode, and an optical filter 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 optical filter (on the side closer to the substrate), or a configuration in which the light-gathering means is provided on the optical filter. In addition, the optical filter may have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, a low refractive index is preferable for each colored pixel of the partitions. The imaging device equipped with the solid-state image sensor of the present invention can be used in digital cameras, electronic devices with imaging functions (mobile phones, smartphones, etc.), as well as in automotive cameras and surveillance cameras. [Examples]

[0102] 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".

[0103] Prior to the examples, each measurement method will be described. The methods for measuring the weight-average molecular weight (Mw), number-average molecular weight (Mn), and acid value (mgKOH / g) of resins are as follows.

[0104] (Average molecular weight of resin (D)) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of resin (D) were measured by gel permeation chromatography (GPC) equipped with an RI 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. The oven temperature was 40°C, tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. Molecular weights are expressed on a polystyrene basis.

[0105] (Acid value of resin (D)) 0.5 to 1 g of resin (D) 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 (mgKOH / g). The acid value per unit of total solids in the resin was then calculated from the acid value of the resin solution and the total solids concentration of the resin solution.

[0106] <Manufacturing of coloring agent (A)> (Manufacturing of micronized pigment A-1) 500 parts of diketopyrrolopyrrole-based red pigment CI Pigment Red 254 (BASF Japan's "Irgajin Red L 3630"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain finely ground pigment (A-1).

[0107] (Manufacturing of micronized pigment A-2) 120 parts of CI Pigment Green 36 (Toyo Color Co., Ltd.'s "Lionol Green 6YK"), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 12 hours. 5000 parts of this mixture were added to warm water and stirred for 1 hour while heating to approximately 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C overnight and then pulverized to obtain finely ground pigment (A-2).

[0108] (Manufacturing of micronized pigment A-3) 100 parts of CI Pigment Green 58 (DIC's FASTOGEN Green A110), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This mixture was added to 3,000 parts of warm water and stirred in a high-speed mixer for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight and then pulverized to obtain fine pigment (A-3).

[0109] (Manufacturing of micronized pigment A-4) 100 parts of CI Pigment Green 63, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture was added to warm water and stirred in a high-speed mixer for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight and then pulverized to obtain fine pigment (A-4).

[0110] (Manufacturing of micronized pigment A-5) 100 parts of CI Pigment Blue 15:6 (Toyo Color Co., Ltd. "Lionol Blue ES"), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. 3,000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to approximately 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours and then pulverized to obtain finely ground pigment (A-5).

[0111] (Manufacturing of micronized pigment A-6) 100 parts of yellow pigment CI Pigment Yellow 139 (BASF Japan's "Paliotol Yellow D1819"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain finely ground pigment (A-6).

[0112] (Manufacturing of micronized pigment A-7) 100 parts of yellow pigment CI Pigment Yellow (LANXESS "Yellow Pigment E4GN"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain finely ground pigment (A-7).

[0113] (Manufacturing of finely milled pigment A-8) 200 parts of CI Pigment Yellow 185 (BASF's "Paliotol Yellow L 1155"), 1000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 100°C for 6 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain finely ground pigment (A-8).

[0114] (Manufacturing of micronized pigment A-9) 100 parts of CI Pigment Violet 23 (Toyo Color Co., Ltd. "Lionogen Violet FG6140"), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. 3,000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to approximately 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours and then pulverized to obtain finely ground pigment (A-9).

[0115] <Manufacturing of resin (D)> (Resin (D1-1) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 7 parts of 3-mercapto-1,2-propanediol, 10.3 parts of pyromellitic dianhydride, 40 parts of propylene glycol monomethyl ether acetate, and 0.1 parts of monobutyltin oxide as a catalyst were charged. 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 groups were half-esterified. Next, 30 parts of 2-hydroxypropyl methacrylate, 30 parts of methoxyethyl acrylate, 20 parts of t-butyl acrylate, 5 parts of methacrylic acid, 15 parts of methyl methacrylate, and 65 parts of propylene glycol monomethyl ether acetate were charged. The reaction vessel was heated to 80°C, and 0.1 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the mixture was reacted for 12 hours (second step). Total solids measurement confirmed that 95% had reacted. Finally, 36 parts of 2-methacryloyloxyethyl isocyanate and 0.1 parts of hydroquinone were added to the compound obtained in the second step, and the reaction was carried out by IR until the disappearance of the 2270 cm-1 peak based on the isocyanate group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the total solids content was adjusted with propylene glycol monomethyl ether acetate to obtain a resin (D1-1) solution with a total solids content of 50%. The acid value of the obtained dispersant was 70 mg KOH / g, and the weight-average molecular weight was 11000.

[0116] The resin (D1-1) solution was synthesized in the same manner as the production example, except that the raw materials and proportions were changed as shown in Table 1, to obtain resin (D1-2) solution and resin (D1-3) solution.

[0117] [Table 1]

[0118] (Resin (D2-1) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 50.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and 70.7 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 45.7 parts of propylene glycol monomethyl ether acetate was added, and the mixture was reacted for 10 hours. Total solids content was measured to confirm that 95% had reacted. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. Subsequently, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was complete, propylene glycol monomethyl ether acetate was added to adjust the total solids content to 50% by mass, yielding a resin (D2-1) with an acid value of 110 mg KOH / g and a weight-average molecular weight of 9000.

[0119] The resin (D2-1) solution was synthesized in the same manner as the production example, except that the raw materials and proportions were changed as shown in Table 2, to obtain resin (D2-2) solution and resin (D2-3) solution.

[0120] [Table 2]

[0121] <Manufacturing of other resins D-1 to D-3> (Resin (D-1) solution) In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 333 parts of PGMAc were introduced. After replacing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C. A solution consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc, to which 5.0 parts of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 43.0 parts [0.5 mol, (100 mol%) relative to the glycidyl groups of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours until the total solids acid value reached 1 mg KOH / g, at which point the reaction was terminated. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours to obtain a resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the total solids. PGMAc was added to prepare the resin (D-1) solution so that the total solids content was 50% by mass. The weight-average molecular weight (Mw) was 9,000, and the acid value was 95 mg KOH / g.

[0122] (Resin (D-2) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer into a separable four-neck flask. 333 parts of PGMAc were placed in the vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 35.5 parts glycidyl methacrylate, 12.0 parts methacrylic acid, 20.7 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 2.0 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 2 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 40 minutes to measure the total solids content. PGMAc was then added to prepare resin (D-2) solution so that the total solids content was 50%. The weight-average molecular weight (Mw) was 20,000, and the acid value was 41 mgKOH / g.

[0123] (Resin (D-3) solution) Separable four-neck flus equipped with thermometer, condenser, nitrogen gas inlet, dripping tube and stirring device 370 parts of PGMAc were charged into the flask, the temperature was raised to 80°C, and the flask was purged with nitrogen. Then, a mixture of 18 parts of paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours using a dropping tube. After the dropwise addition, the mixture was reacted at 100°C for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the container was replaced with an air purging system, and 9.3 parts of acrylic acid (100% of the glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the container. The reaction was continued at 120°C for 6 hours until the total solids acid value reached 0.5, at which point the reaction was terminated to obtain an acrylic resin solution. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and the reaction was continued at 120°C for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the total solids. PGMAc was then added to the previously synthesized resin solution to bring the total solids content to 50% by mass to prepare resin (D-3) solution. The weight-average molecular weight (Mw) was 19000, and the acid value was 65 mgKOH / g.

[0124] <Manufacturing of dispersions> (Manufacturing of dispersion 1 of manufacturing example 1) After stirring and mixing the following raw materials until uniform, the mixture was dispersed for 3 hours using an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") with a 0.5 mm diameter zirconia bead. The mixture was then filtered through a 1.0 μm pore size filter to prepare dispersion 1. The organic solvent (O-1) is PGMAc. Micronized pigment (A-1): 13.5 parts Colorant derivative (N-1): 0.5 parts Colorant derivative (N-4): 1.0 part Resin (D1-1) solution: 10.0 parts Organic solvent (O-1): 75.0 parts

[0125] (Manufacturing Examples 2-21) Dispersions 2 to 24 were obtained by varying the types and amounts of ingredients as shown in Tables 3-1 and 3-2.

[0126] [Table 3-1]

[0127] [Table 3-2]

[0128] The colorant derivatives (N) listed in Tables 3-1 and 3-2 have the following structures. Colorant derivative (N-1) [ka]

[0129] Colorant derivative (N-2) [ka]

[0130] Colorant derivative (N-3) [ka]

[0131] Colorant derivative (N-4) [ka]

[0132] Colorant derivative (N-5) [ka]

[0133] <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 0.3 μm to obtain photosensitive composition 1. Dispersion 1: 67.00 parts Dispersion 9: 13.00 parts Oxime ester-based photopolymerization initiator (B-4): 0.50 parts Polymerizable compound (C-1): 3.70 parts Resin (D-2) solution: 1.40 parts Leveling agent (L-1): 0.05 parts Polymerization inhibitor (F-1): 0.05 parts Organic solvent (O-1): 4.30 parts Organic solvent (O-2): 10.00 parts

[0134] [Oxime ester initiator (B)] B-1: Adeka Cruises NCI-831 ·B-2: Irgacure OXE-04 • B-3: Adeka Cruises NCI-730 B-4: Adeka Cruises NCI-930 · B-5: Irgacure OXE-01

[0135] [Polymerizable compound (C)] • C-1: KAYARAD DPEA-12 (Number of ethylenically unsaturated double bond groups: 6) • C-2: Arronix M-460 (Number of ethylenically unsaturated double bonds: 4) • C1-1: Arronix M-350 (Number of ethylenically unsaturated double bonds: 3) • C1-2: Arronix M-360 (Number of ethylenically unsaturated double bonds: 3) • C1-3: Arronix M-310 (Number of ethylenically unsaturated double bonds: 3) • C1-4: Arronix M-321 (Number of ethylenically unsaturated double bonds: 3) • C1-5: NK ester A-GLY-3E (Number of ethylenically unsaturated double bonds: 3) • C1-6:NK ester A-GLY-3P (Number of ethylenically unsaturated double bonds: 3) • C1-7: NK ester ABE-300 (Number of ethylenically unsaturated double bonds: 2)

[0136] [Polymerizable compounds (M) that do not contain alkylene oxide-modified units] · M-1: Aronix M-402

[0137] [Polymerization inhibitor (F)] F-1: Methylhydroquinone

[0138] [Leveling agent (L)] • A mixed solution prepared by dissolving 1 part of L-1:FZ-2122 (manufactured by Toray Dow Corning) in 9 parts of PGMAc.

[0139] [Organic solvent (O)] • O-1: PGMAc (Propylene glycol methyl ether acetate) ·O-2:3-Methoxybutanol

[0140] The ingredients and quantities were varied to achieve the composition ratios shown in Tables 4-1 to 4-5, and photosensitive compositions 2 to 58 of Examples 2 to 55 and Comparative Examples 1 to 3 were obtained.

[0141] <Evaluation of photosensitive compositions> For Examples 1-54 and Comparative Examples 1-3, pixel rectangularity, adhesion, and development residue were evaluated using the following methods. The evaluation results are shown in Tables 4-1 to 4-5.

[0142] [Pixel Rectangle] Each of the photosensitive compositions 1 to 57 was applied by spin coating onto an 8-inch (203.2 mm) silicon wafer with an undercoat layer to a film thickness of 0.5 μm after coating. Next, post-bake was performed at 100°C for 90 seconds using a hot plate. Then, pulse exposure was performed using an i-line stepper exposure machine through a mask with a 1.0 μm square Bayer pattern under the following conditions. Next, paddle development was performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Afterward, rinsing was performed with a spin shower, followed by washing with pure water. Finally, pixels (patterns) were formed by heating (post-bake) at 220°C for 3 minutes using a hot plate. The cross-sectional shape of the pixels was observed using an electron microscope (JEOL Ltd. JSM-IT200), and the angle (θ) between the silicon wafer and the edge of the pattern cross-section was measured. If this angle deviates significantly from 90 degrees, color mixing with adjacent pixels may occur. The exposure conditions and their rankings are as follows: Exposure conditions: i-line (wavelength 365nm), average illuminance: 20000W / m 2 Exposure dose 3000 J / m 2 <Rating Rank> 4: 87° ≤ θ ≤ 93° 3: 84° ≤ θ < 87° or 93° < θ ≤ 96° 2: 81° ≤ θ < 84° or 96° < θ ≤ 99° 1: θ ≤ 81° or θ > 99° A rating of 2 or higher indicates a usable range.

[0143] [Adhesion] Each of the photosensitive compositions 1 to 57 was applied by spin coating onto an 8-inch (203.2 mm) silicon wafer with an undercoat layer to a film thickness of 0.5 μm after coating. Next, post-bake was performed at 100°C for 90 seconds using a hot plate. Then, exposure was performed using an i-line stepper exposure machine through a mask having a single-pixel pattern on all four sides in 0.2 μm increments from 0.6 μm to 2.0 μm under the following conditions. Next, paddle development was performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). After that, rinsing was performed with a spin shower and then washed with pure water. Next, pixels (patterns) were formed by heating (post-bake) at 220°C for 3 minutes using a hot plate, and the remaining patterns were confirmed. Exposure conditions: i-line (wavelength 365nm), average illuminance: 20000W / m 2 Exposure dose 3000 J / m 2 For the evaluation substrate, single-pixel patterns with a width of 0.6 to 2.0 μm were observed using an optical microscope to confirm the minimum line width of the remaining fine-line patterns. <Rating Rank> A pattern of 4:0.6μm remains. 3: Fine lines smaller than 1.0 μm remain. 2: Fine lines smaller than 2.0 μm remain. No fine lines smaller than 1:2.0 μm remain. A rating of 2 or higher is considered usable.

[0144] [Developing residue] Each of the photosensitive compositions 1 to 57 was applied by spin coating onto an 8-inch (203.2 mm) silicon wafer with an undercoat layer to a film thickness of 0.5 μm after coating. Next, post-bake was performed at 100°C for 90 seconds using a hot plate. Then, pulse exposure was performed using an i-line stepper exposure machine through a mask with a 1.0 μm square Bayer pattern under the following conditions. Next, paddle development was performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Afterward, rinsing was performed with a spin shower, followed by washing with pure water. Finally, pixels (patterns) were formed by heating (post-bake) at 220°C for 3 minutes using a hot plate, and the developed unexposed areas between pixels were observed and evaluated using an electron microscope (JEOL Ltd. JSM-IT200). The exposure conditions and evaluation ranks are as follows. <Rating Rank> 4: There is absolutely no residue in the unexposed areas. 3: Resist residue less than 0.1 μm in width was observed in the unexposed area. 2: A residue with a width of 0.1 to 0.2 μm was observed in the unexposed area. 1: Resist residue with a width greater than 0.2 μm in the unexposed area is observed. A rating of 2 or higher indicates a usable range.

[0145] [Table 4-1]

[0146] [Table 4-2]

[0147] [Table 4-3]

[0148] [Table 4-4]

[0149] [Table 4-5] [Explanation of Symbols]

[0150] 10 LCD display device 11 Transparent substrate 12 TFT arrays 13 Transparent electrode layer 14. Orientation layer 15 Polarizing plates 21 Transparent substrate 23 Transparent electrode layer 24 orientation layer 25 Polarizing plates 30 backlight units 31 White LED light source LC LCD

Claims

1. A photosensitive composition comprising a colorant (A), an oxime ester-based photopolymerization initiator (B), a polymerizable compound (C), and a resin (D), The content of the coloring agent (A) is 50% by mass or more and 70% by mass or less of the total solid content of the photosensitive composition by 100% by mass. The polymerizable compound (C) has an alkylene oxide modified unit and an ethylenically unsaturated double bond group, A photosensitive composition characterized in that the resin (D) comprises a resin (D1) having a urethane bond and an ethylenically unsaturated double bond group and a molecular weight of 10,000 or more and 30,000 or less.

2. The photosensitive composition according to claim 1, characterized by containing a polymerizable compound (C1) having three or fewer ethylenically unsaturated double bond groups.

3. The photosensitive composition according to claim 1, characterized in that resin (D) further comprises resin (D2) (excluding resin (D1)) having an acid value of 100 mg KOH / g or more and 150 mg KOH / g or less.

4. The photosensitive composition according to claim 3, characterized in that the total solid content of a resin (D1) having urethane bonds and ethylenically unsaturated double bond groups and a molecular weight of 10,000 to 30,000, and a resin (D2) having an acid value of 100 mg KOH / g to 150 mg KOH / g, is 80% to 99% by mass of the total solid content of resin (D) by 100% by mass.

5. An optical filter manufactured using a photosensitive composition as described in any one of claims 1 to 4.

6. A display element using the optical filter described in claim 5.

7. A solid-state image sensor using the optical filter described in claim 5.

Images