Visible light-shielding photosensitive composition, cured film, optical filter, image display device, solid-state image sensor, and infrared sensor

Abstract

The present invention aims to provide a visible light-shielding photosensitive composition characterized by excellent light-shielding properties in the visible light region of 400 to 700 nm wavelength, excellent alkaline developability and pattern adhesion, and containing a high concentration of a colorant, as well as a cured film, optical filter, image display device, solid-state image sensor, and infrared sensor using the same. [Solution] A visible light-shielding photosensitive composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the content of the colorant (A) is 50% by mass or more of the total solids, and the colorant (A) contains copper phthalo-blue pigment, CIPY139, and CIPV23 in predetermined amounts, the resin (B) comprises a resin (B1) having an aromatic carboxylic acid moiety and a vinyl polymer moiety, the content of the resin (B1) is 80% by mass or more of the total solids of the resin (B), and the polymerizable compound (C) comprises a polymerizable compound (C1) having a chain with two or more repeating units of ethyleneoxy groups.

Description

Technical Field

[0001] The present invention relates to a visible light-shielding photosensitive composition, a cured film, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor.

Background Art

[0002] The cured film is formed by arranging two or more 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 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 a cured film, a method called a pigment dispersion method using 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, a cured film is manufactured by the following method. First, a photosensitive colored 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 the cured film.

[0003] In recent years, near-infrared rays, which have a longer wavelength and are less likely to be scattered than visible light, have been applied to sensing such as distance measurement and three-dimensional measurement. In addition, since near-infrared rays are invisible to the eyes of humans, animals, etc., they can also be used for applications such as photographing nocturnal wild animals and photographing without stimulating the subject for security purposes. Therefore, the development of a cured film capable of transmitting near-infrared rays with less noise derived from visible light is desired.

[0004] Patent Document 1 discloses an example of a coloring composition using three or more organic pigments, in which a polymerizable compound having a chain with two or more repeating alkylene oxy units is used. However, when the pigment concentration is increased to improve visible light shielding, there is a problem in that alkaline developability decreases, resulting in poor development residue and pattern adhesion. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2015 / 182277 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a visible light-shielding photosensitive composition characterized by excellent light-shielding properties in the visible light region of 400 to 700 nm wavelength, excellent alkaline developability and pattern adhesion, and containing a high concentration of a colorant, as well as a cured film, optical filter, image display device, solid-state image sensor, and infrared sensor using the same. [Means for solving the problem]

[0007] The present invention relates to a visible light-shielding photosensitive composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the colorant (A) contains 20 to 50% by mass of copper phthalocyanine blue pigment, 20 to 50% by mass of CI pigment yellow 139, and 15 to 45% by mass of CI pigment violet 23, per 100% by mass of colorant (A), and the total content of the colorant (A) is 50% by mass or more of the total solid content of the visible light-shielding photosensitive composition; the resin (B) comprises a resin (B1) having an aromatic carboxylic acid moiety and a vinyl polymer moiety, and the content of the resin (B1) is 80% by mass or more of the total solid content of the resin (B); and the polymerizable compound (C) comprises a polymerizable compound (C1) having a chain with two or more repeating units of ethyleneoxy groups.

[0008] The present invention also relates to the visible light-shielding photosensitive composition wherein the copper phthalocyanine blue pigment is one or more selected from the group consisting of CI pigment blue 15:3, 15:4, and 15:6.

[0009] The present invention also relates to the visible light-shielding photosensitive composition, characterized in that the resin (B1) comprises a resin (B1-1) containing a (meth)acryloyl group-containing vinyl polymer moiety, and the content of resin (B1-1) is 50% by mass or more with respect to the total solid content of resin (B1).

[0010] The present invention also relates to the visible light-shielding photosensitive composition, characterized in that resin (B1) comprises resin (B1-2) which does not contain a (meth)acryloyl group-containing vinyl polymer moiety, and the acid value of resin (B1-2) is 100 mg KOH / g or more.

[0011] The present invention also relates to the visible light-shielding photosensitive composition wherein the photopolymerization initiator (D) contains a compound represented by the following general formula (1). General formula (1) [ka] [In formula (1), X1 to X6 represent a hydrogen atom, a cyclic, linear, or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group.]

[0012] The present invention also relates to a cured film produced from the visible light-shielding photosensitive composition.

[0013] The present invention also relates to an optical filter having the cured film.

[0014] The present invention also relates to an image display device having the cured film.

[0015] The present invention also relates to a solid-state imaging device having the cured film.

[0016] The present invention also relates to an infrared sensor having the cured film. [Effects of the Invention]

[0017] According to the present invention, there are provided a visible light-shielding photosensitive composition containing a high concentration of a colorant, which is excellent in light-shielding properties in the visible light region of wavelengths 400 to 700 nm, and excellent in alkali developability and pattern adhesion, and a cured film, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor using the same. [Brief Description of the Drawings]

[0018] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device. [Figure 2] FIG. 2 is a schematic cross-sectional view of an infrared sensor. [Embodiments for Carrying Out the Invention]

[0019] The terms used in this specification are defined. When expressed as “(meth)acryloyl,” “(meth)acryl,” “(meth)acrylic acid,” “(meth)acrylate,” or “(meth)acrylamide,” unless otherwise specified, they represent “acryloyl and / or methacryloyl,” “acryl and / or methacryl,” “acrylic acid and / or methacrylic acid,” “acrylate and / or methacrylate,” and “acrylamide and / or methacrylamide,” respectively. “C.I.” listed in this specification means Color Index (C.I.). The colorant includes pigments and dyes. The light-shielding property refers to the function of blocking visible light. The resin includes resin-type dispersants, binder resins, thermoplastic resins, and thermosetting compounds.

[0020] (Visible light-shielding photosensitive composition) The visible light-shielding photosensitive composition in the present invention is a visible light-shielding photosensitive composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), where the colorant (A) contains 20 to 50% by mass of a copper phthalocyanine blue pigment, 20 to 50% by mass of C.I. Pigment Yellow 139, and 15 to 45% by mass of C.I. Pigment Violet 23 in 100% by mass of the colorant (A), the total content of the colorant (A) is 50% by mass or more based on the total solid content of the visible light-shielding photosensitive composition, the resin (B) contains a resin (B1) having an aromatic carboxylic acid site and a vinyl polymer site, the content of the resin (B1) is 80% by mass or more based on the total solid content of the resin (B), and the polymerizable compound (C) contains a polymerizable compound (C1) having a chain with a repeating unit number of 2 or more of an ethyleneoxy group.

[0021] 〈Colorant A〉 The colorant (A) in the present invention contains 20 to 50% by mass of copper phthalocyanine blue pigment, 20 to 50% by mass of CI pigment yellow 139, and 15 to 45% by mass of CI pigment violet 23 in 100% by mass of colorant (A), and the total content of colorant (A) is 50% by mass or more of the total solid content of the visible light-shielding photosensitive composition. Visible light shielding properties can be obtained by having the content of each pigment in 100% by mass of colorant (A), and the total content of colorant (A), within the above ranges. Colorant (A) may contain other organic pigments, dyes, and inorganic pigments as needed. Furthermore, the content of each pigment in 100% by mass of colorant (A) is preferably 30-45% by mass of copper phthalocyanine blue pigment, 30-45% by mass of CI pigment yellow 139, and 15-35% by mass of CI pigment violet 23. When the content of each pigment in 100% by mass of colorant (A) is within the above range, it is more effective in improving the light-shielding properties, especially on the longer wavelength side of the visible light region.

[0022] (Blue organic pigment: copper phthalocyanine blue pigment) Examples of copper phthalocyanine blue pigments include CI Pigment Blue 15:1, 15:2, 15:3, 15:4, and 15:6. In particular, it is preferable that one or more are selected from the group consisting of CI Pigment Blue 15:3, 15:4, and 15:6, with CI Pigment Blue 15:3 being more preferable.

[0023] (Yellow organic pigment) Other yellow pigments that can be used in conjunction with CI Pigment Yellow 139 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, The following can be listed: 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 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, and 233.

[0024] (Purple organic pigment) Other purple organic pigments that can be used in combination with CI Pigment Violet 23 include, for example, CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0025] (Other organic pigments) Other specific examples of organic pigments are shown below by their color index numbers.

[0026] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57: 2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, and 296 can be listed.

[0027] Examples of orange organic pigments include CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73.

[0028] 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.

[0029] 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.

[0030] (Inorganic pigments) In addition, inorganic pigments include, for example, 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.

[0031] <Pigment miniaturization> When using organic pigments as colorants, it is preferable to mix them with other raw materials after micronization. Examples of micronization methods include wet grinding, dry grinding, and dissolution extraction. Among these, salt milling by the kneader method, a type of wet grinding, is preferred. The average primary particle size of the organic pigment after micronization is preferably 10 to 80 nm, and more preferably 15 to 70 nm. An appropriate particle size further improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of approximately 20 particles arbitrarily selected from a magnified image obtained using a TEM (transmission electron microscope). If the particle has both a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0032] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using batch or continuous kneading machines such as kneaders, two-roll mills, three-roll mills, ball mills, attritors, sand mills, and planetary mixers, and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0033] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the standpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of pigment, considering both processing efficiency and production efficiency.

[0034] The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (miscible) in water but substantially does not dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling point solvent with a boiling point of 120°C or higher, as it does not easily volatilize due to the temperature rise during salt milling. Examples of water-soluble organic solvents include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0035] During the salt milling process, a resin may be added as needed. Examples of resins include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in water-soluble organic solvents. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of pigment.

[0036] <Metal Removal> If specific metal elements are present in large quantities as impurities other than the pigment components in a visible light-shielding photosensitive composition, it can impair the dispersion stability over time, and may also lead to a decrease in heat resistance or sensitivity. Furthermore, cured films made using such compositions may have foreign matter formation, which can easily result in a decrease in brightness. It is preferable that the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) in the visible light-shielding photosensitive composition is 500 ppm by mass or less.

[0037] The total amount of specific metal elements contained in the visible light-shielding photosensitive composition of the present invention is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. The lower limit of the total amount of specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, a visible light-shielding photosensitive composition can be obtained that can suppress costs, has excellent storage stability, and forms a cured film with little generation of foreign matter and little reduction in brightness.

[0038] The amount of each specific metal element contained in the visible light-shielding photosensitive composition of the present invention is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0039] Furthermore, it is preferable that the metals that make up the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, contain fewer impurities that do not function effectively, and these can be removed in the same way as specific metal elements by the following method. In addition, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc., that have been introduced due to materials (such as catalysts) used in the manufacturing process of the various raw materials for the visible light-shielding photosensitive composition be low.

[0040] Methods for removing colorants (A) or metals introduced from equipment during the manufacturing process include washing with water as described in Japanese Patent Publication No. 2010-83997, Japanese Patent Publication No. 2018-36521, Japanese Patent Publication No. Hei 7-198928, Japanese Patent Publication No. Hei 8-333521, Japanese Patent Publication No. 2009-7432, etc., and methods for removing magnetic foreign matter using a magnet as described in Japanese Patent Publication No. 2011-48736, and one or more of these methods may be used as appropriate.

[0041] The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0042] <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. Also included are derivatives of dyes and lake pigments, which are dyes that have been transformed into lakes.

[0043] Furthermore, examples of dyes include acidic dyes having acidic groups such as sulfonic acid and carboxylic acid; in the case of direct dyes, inorganic salts of acidic dyes; salt-forming compounds of acidic dyes with quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds; and salt-forming compounds such as acidic dyes with resin components having amino groups. Salt-forming compounds of acidic dyes with compounds having an onium base are also preferred due to their excellent fastness. In addition, the compounds having an onium base are preferably resins having cationic groups in their side chains.

[0044] Basic dyes include salt-forming compounds made from organic acids, perchloric acid, or metal salts thereof. Among salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various substances and compatibility with pigments.

[0045] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), and quinoneimine dyes (oxazine dyes). Examples include dyes such as thiazine dyes, 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. 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 from the viewpoint of color characteristics such as hue, color separation, and color unevenness, with xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes being more preferred. The specific structures of the dyes are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Pigment Handbook" (edited by Okawara et al.; Kodansha, 1986), among others.

[0046] <Dye derivatives> Dye derivatives may be used in visible light-shielding photosensitive compositions as needed. Dye derivatives are compounds having acidic groups, basic groups, neutral groups, etc., in organic dye residues. Examples of dye derivatives include compounds having acidic substituents such as sulfo groups, carboxyl groups, or phosphate groups, as well as compounds having basic substituents such as amine salts thereof, 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.

[0047] Specifically, diketopyrrolopyrrole dye derivatives are described in Japanese Patent Publication No. 2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, and Japanese Patent Publication No. 2017-156397; phthalocyanine dye derivatives are described in Japanese Patent Publication No. 2007-226161, WO2016 / 163351, Japanese Patent Publication No. 2017-165820, and Japanese Patent No. 5753266; and anthraquinone dye derivatives are described in Japanese Patent Publication No. Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, Brochure WO2009 / 025325, Quinacridone-based dye derivatives are Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, Dioxazine-based dye derivatives are Japanese Patent Publication No. 2011-162662, Thiazine-indigo-based dye derivatives are Japanese Patent Publication No. 2007-3147 Japanese Patent Publication No. 85, Triazine-based dye derivatives are described in 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, Japanese Patent Publication No. 2007-314681, Benzoisoindole-based dye derivatives are described in Japanese Patent Publication No. 2009-57478, Quinophthalone-based dye derivatives are described in Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, Japanese Patent Publication No. 2 Examples of dye derivatives include those described in Japanese Patent Publication No. 012-226110, those described in Japanese Patent Publication Nos. 2012-208329 and 2014-5439 for naphthol-based dye derivatives, those described in Japanese Patent Publication Nos. 2001-172520 and 2012-172092 for azo-based dye derivatives, those described in Japanese Patent Publication Nos. 2004-307854 for acidic substituents, and those described in Japanese Patent Publication Nos. 2002-201377, 2003-171594, 2005-181383 and 2005-213404 for 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.

[0048] These dye derivatives can be used individually or in combination of two or more types.

[0049] The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of pigment.

[0050] By adding a pigment derivative to a pigment and performing pigmentation treatments such as acid basting, acid slurry, dry milling, salt milling, or solvent-salt milling, the pigment derivative is adsorbed onto the pigment surface, making the primary particles of the pigment finer compared to when no pigment derivative is added.

[0051] By adding a dye derivative to the pigment and performing dispersion treatments such as wet dispersion using two-roll, three-roll, or bead-based processes, the dye derivative is adsorbed onto the pigment surface, giving the pigment surface polarity and promoting the adsorption of resin-type dispersants. This improves compatibility with the pigment, dye derivative, resin-type dispersant, solvent, and other additives, resulting in improved dispersion stability and viscosity stability over time when used as a visible light-shielding photosensitive composition. Furthermore, the improved compatibility leads to excellent film stability over time when the colored curable composition is coated onto a glass substrate, resulting in good stability and property dependence of pattern shape, etc., on the waiting time from coating to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay), as well as good line width sensitivity stability. In addition, the adsorption and coating of the pigment surface with the dye derivative and resin-type dispersant suppresses pigment aggregation and crystal precipitation due to sublimation when the coating film is heated and fired. Furthermore, variations in development time and development residue are also suppressed.

[0052] <Resin (B)> The resin (B) in the present invention comprises a resin (B1) having an aromatic carboxylic acid moiety and a vinyl polymer moiety, characterized in that the content of resin (B1) is 80% by mass or more relative to the total solid content of resin (B). This results in excellent pattern resolution and developability even when containing a high concentration of colorant. Furthermore, it is preferable that resin (B1) comprises a resin (B1-1) containing a (meth)acryloyl group-containing vinyl polymer moiety, and the content of resin (B1-1) is 50% by mass or more relative to the total solid content of resin (B1). This further improves pattern resolution. Furthermore, it is preferable that resin (B1) comprises a resin (B1-2) that does not contain a (meth)acryloyl group-containing vinyl polymer moiety and has an acid value of 100 mgKOH / g or more. This further improves developability. Furthermore, resin (B) may also include resin (B2) having either an aromatic carboxylic acid moiety or a vinyl polymer moiety.

[0053] (Resin having aromatic carboxylic acid moieties and vinyl polymer moieties (B1)) The resin (B1) having aromatic carboxylic acid moieties and vinyl polymer moieties can be manufactured by known methods such as those described in WO2008 / 007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007-23195, and JP 1996-143651.

[0054] A particularly preferred example of the resin (B1) having an aromatic carboxylic acid moiety and a vinyl polymer moiety is one having a main chain containing an aromatic carboxylic acid ester moiety having an ester bond obtained by esterifying an aromatic compound having two or more acid anhydride groups with a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety. The ratio of acid anhydride groups to 1 mole of hydroxyl groups is 0.9 to 1.5 moles, preferably 1.0 to 1.3 moles.

[0055] Furthermore, the main chain containing the aromatic carboxylic acid ester moiety has a structure having a encapsulation site derived from a monoalcohol, which will be described later. That is, the acid anhydride group remaining in the main chain is ring-opened with a monoalcohol, resulting in the presence of an alcohol ester group and a carboxyl group. By using such resins, the filterability of the visible light-shielding photosensitive composition is improved, the generation of foreign matter in the coating film formed by coating the visible light-shielding photosensitive composition is suppressed, and furthermore, when coating the visible light-shielding photosensitive composition, the resolubility of the solidified material derived from the visible light-shielding photosensitive composition formed in the coating apparatus in propylene glycol monomethyl ether acetate is improved, thus improving productivity.

[0056] In this invention, the side chains containing the vinyl polymer moiety are formed by polymerization of ethylenically unsaturated monomers.

[0057] The side chains containing the vinyl polymerized moiety are obtained by polymerizing a vinyl polymerizable compound in the presence of a compound having a thiol group. When a compound having two hydroxyl groups and one thiol group in its molecule is used as the compound having the thiol group, the main chain is formed after the side chain is formed. Furthermore, if the compound having the thiol group is the main chain after the esterification reaction (which has multiple thiol groups derived from a compound having two hydroxyl groups and one thiol group in its molecule), then side chains are formed after the main chain is formed. Furthermore, the total monomer units constituting the vinyl polymer portion refer to the substructures derived from each ethylenically unsaturated monomer after vinyl polymerization.

[0058] (Aromatic compounds having two or more acid anhydride groups) Aromatic compounds having two or more acid anhydride groups include, for example, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 2,3,6,7-naphthalene Tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether Examples include dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride.

[0059] (Compounds having two or more hydroxyl groups) As described above, compounds having two or more hydroxyl groups are preferably compounds having a hydroxyl group and a thiol group in the molecule, and more preferably compounds having two hydroxyl groups and one thiol group in the molecule.

[0060] Examples of compounds having two hydroxyl groups and one thiol group in their molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0061] (Monoalcohol) Monoalcohols include, for example, methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, and other monoalcohols. Monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, etc. Examples include monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. These can be used individually or in combination of two or more.

[0062] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The dispersant may have an ether group or a carbonyl group at the end of its main chain, improving the resolubility of the dispersant in PGMAc. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0063] The main chain, which is an aromatic carboxylic acid ester moiety, may have encapsulation sites derived from monoalcohols, as well as encapsulation sites formed by reaction with water.

[0064] Regarding the synthesis of the encapsulation site, the amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 molar equivalents, and more preferably 1.5 to 20 molar equivalents, per equivalent of acid anhydride group remaining in the main chain. If the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability. If the amount is 30 molar equivalents or less, transesterification reactions due to ester bonding between the monoalcohol and the dispersant are less likely to occur, and a decrease in molecular weight is less likely to occur.

[0065] (Vinyl polymer moiety having a (meth)acryloyl group) The vinyl polymer moiety containing (meth)acryloyl groups in resin (B1-1), which includes a vinyl polymer moiety containing (meth)acryloyl groups, can be synthesized by reacting the hydroxyl groups of the vinyl polymer moiety with isocyanate groups in an isocyanate group-containing monomer. This allows for the production of a photocurable vinyl polymer moiety.

[0066] Examples of isocyanate group-containing monomers include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0067] <Binder resin> The visible light-shielding photosensitive compositions described herein may include a binder resin. The binder resin is a resin that, when a film with a thickness of 1.0 μm is formed, has a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm in the thickness direction of the film. Preferably, the transmittance in the entire wavelength range of 400 to 700 nm is 95% or more. In terms of curability, examples of binder resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins. The active energy ray curable resin may be a thermoplastic resin or a thermosetting resin having an active energy ray reactive functional group. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting developability in the alkali development process during the production of the cured film, and an acidic group is required. These can be used individually or in combination of two or more types.

[0068] (thermoplastic resin) Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclic rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of alkali-soluble thermoplastic resins include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of alkali-soluble thermoplastic resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred in terms of improved developability, heat resistance, and transparency.

[0069] <Thermosetting compounds> In the present invention, a thermosetting compound may be included. When a cured film is produced using the visible light-shielding photosensitive composition for cured films of the present invention, the inclusion of a thermosetting compound reacts during the firing of the filter segment, increasing the crosslinking density of the coating film. This improves the heat resistance of the filter segment, suppresses pigment aggregation during the firing of the filter segment, and improves the contrast ratio.

[0070] The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is not limited thereto.

[0071] (Activated energy ray curable resin) Active energy ray curable resins preferably have ethylenically unsaturated double bonds. Ethyleneenly unsaturated double bonds can be introduced, for example, by the method shown in (i) or (ii) below. Curing with active energy rays causes the resin to undergo three-dimensional crosslinking, increasing the crosslinking density and improving chemical resistance.

[0072] [Method (i)] Method (i) involves, for example, adding a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. Then, the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0073] 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. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0074] 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.

[0075] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Furthermore, if necessary, such as increasing 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.

[0076] Other monomers include the following: For example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate. Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or styrenes such as acryloylmorpholine, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

[0077] 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-maleimide Examples include imidobenzoates, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimidehexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimideacridine, and other N-substituted maleimides; EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0078] A method similar to method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, to which an ethylenically unsaturated monomer having an epoxy group is added to some of the side chain carboxyl groups of the copolymer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0079] [Method (ii)] Method (ii) involves reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the isocyanate group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0080] Examples of ethylenically unsaturated monomers having hydroxyl groups include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferable to use a material having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0081] Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0082] Other monomers that can constitute alkali-soluble resins include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkylene oxy group-containing monomers, phosphate ester group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like. N-substituted maleimides include, for example, cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 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-( Examples include 2,4,6-trichlorophenyl)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. Examples of alkylene oxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0083] For carboxyl group-containing ethylenically unsaturated monomers, the monomers already described can be used.

[0084] Phosphate ester group-containing ethylenically unsaturated monomers are, for example, compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0085] (Alkali-soluble resin without ethylenically unsaturated double bonds) The visible light-shielding photosensitive compositions described herein may contain an alkali-soluble resin that does not have an ethylenically unsaturated double bond in order to adjust the degree of curing of the coating.

[0086] In this invention, the weight-average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, and more preferably 4,000 to 20,000, in order to impart alkali-developable solubility. Furthermore, the Mw / Mn value is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain. If it exceeds 40,000, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. In this invention, the acid value of the alkali-soluble resin is 50 to 200 (KOH mg / g) to impart alkali-developable solubility, preferably in the range of 70 to 180, and more preferably in the range of 90 to 170. If the acid value is less than 50, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. If it exceeds 200, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain.

[0087] Each raw material used in the synthesis of the binder resin can be used individually or in combination of two or more types.

[0088] <Polymerizable compound (C)> Polymerizable compound (C) is a monomer or oligomer containing a polymerizable unsaturated group. Examples of polymerizable unsaturated groups include vinyl groups, (meth)acryloyl groups, and (meth)allyl groups. Oligomers are compounds with a molecular weight of 1000 or more. From the viewpoint of sensitivity, polymerizable compound (C) is preferably a compound having one or more polymerizable unsaturated groups, and more preferably a compound having two or more polymerizable unsaturated groups. Among these, polyfunctional polymerizable compounds having three or more polymerizable unsaturated groups are even more preferred.

[0089] (Polymerizable compound (C1) containing an ethylene oxy chain) The polymerizable compound (C) in the present invention is characterized by containing polymerizable compound (C1) having a chain with two or more repeating ethyleneoxy units. As a result, the solubility in alkaline developer is increased due to the action of the ethyleneoxy chain, and developing residue can be suppressed. In the present invention, the ethylene oxy chain preferably has 2 to 10 repeating units, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 2. The ethylene oxy group is preferably unsubstituted. Furthermore, polymerizable compound (C) may include polymerizable compounds that do not contain chains with two or more repeating ethyleneoxy groups.

[0090] In the present invention, as the polymerizable compound (C1) having a chain with two or more repeating ethyleneoxy units, for example, at least one selected from the group of compounds represented by the following general formulas (Z-1) or (Z-2) may be used.

[0091] [ka]

[0092] In general formulas (Z-1) and (Z-2), E independently represents -(C2H4O)-, and X independently represents an acryloyl group, a metachloroyl group, a hydrogen atom, or a carboxyl group. In general formula (Z-1), the total number of acryloyl groups and metacloyl groups is 3 or 4, each m independently represents an integer from 0 to 10, at least one of the m represents an integer from 2 to 10, and the sum of the m values ​​is an integer from 2 to 40. In general formula (Z-2), the total number of acryloyl groups and metacloyl groups is 5 or 6, each m independently represents an integer from 0 to 10, at least one of the m represents an integer from 2 to 10, and the sum of the m values ​​is an integer from 2 to 60.

[0093] In the general formula (Z-1), m is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4. The sum of m is preferably an integer between 2 and 40, more preferably an integer between 2 and 16, and particularly preferably an integer between 4 and 8. In the general formula (Z-2), m is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4. Furthermore, the sum of m is preferably an integer between 3 and 60, more preferably an integer between 3 and 24, and particularly preferably an integer between 6 and 12. Furthermore, in general formula (Z-1) or general formula (Z-2), the -(C2H4O)- is preferably in a form where the end on the oxygen atom side is bonded to X.

[0094] Compounds represented by general formula (Z-1) or general formula (Z-2) may be used individually or in combination of two or more. In particular, the form in general formula (Z-2) in which all six X groups are acryloyl groups is preferred.

[0095] Compounds represented by general formula (Z-1) or general formula (Z-2) can be synthesized by conventionally known steps: a step of attaching an open-ring skeleton to pentaerythritol or dipentaerythritol by a ring-opening addition reaction with ethylene oxide; and a step of introducing a (meth)acryloyl group to the terminal hydroxyl group of the open-ring skeleton by reacting it with, for example, (meth)acryloyl chloride. Each step is well known, and those skilled in the art can easily synthesize compounds represented by general formula (Z-1) or general formula (Z-2).

[0096] Among the compounds represented by general formula (Z-1) or general formula (Z-2), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

[0097] Examples of commercially available polymerizable compounds represented by general formula (Z-1) or general formula (Z-2) include DPEA-12, a hexafunctional acrylate with six ethylene oxy chains, manufactured by Nippon Kayaku Co., Ltd.; RP-1040, a tetrafunctional acrylate with four ethylene oxy chains; and Aronics M-360, a trifunctional acrylate with three ethylene oxy chains, manufactured by Toagosei Co., Ltd.

[0098] The polymerizable compound (C) used in the visible light-shielding photosensitive composition of the present invention preferably contains 50 to 100% by mass of the polymerizable compound (C1) having a chain with two or more repeating units of ethylene oxy groups, more preferably 80 to 100% by mass, and even more preferably 95 to 100% by mass, based on the total amount of polymerizable compound (C), and is particularly preferably composed only of polymerizable compounds having ethylene oxy chains.

[0099] The visible light-shielding photosensitive composition of the present invention may contain polymerizable compounds other than the polymerizable compound (C1) having a chain with two or more repeating ethyleneoxy groups (hereinafter referred to as "other polymerizable compounds"). There are no particular limitations on the other polymerizable compounds, and conventionally known polymerizable compounds can be used. Examples include monomers containing acid groups, monomers containing urethane bonds, and other monomers.

[0100] (Acid group-containing monomer) Examples of acidic groups in acidic monomers include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0101] Examples of acid group-containing monomers include esters of polyhydric alcohols and (meth)acrylic acid-containing poly(meth)acrylates with free hydroxyl groups and dicarboxylic acids; and esters of polyhydric acids and monohydroxyalkyl (meth)acrylates. Specific examples include monoesterified compounds containing free carboxyl groups between monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and oligoesterified compounds containing free carboxyl groups between tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0102] (Urethane bond-containing monomer) Examples of urethane bond-containing monomers include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate.

[0103] Examples of hydroxyl group-containing (meth)acrylates 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 propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0104] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0105] (Other monomers) Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pe Examples include tetraerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, various acrylic acid esters and methacrylic acid esters such as methylolated melamine (meth)acrylate, epoxy(meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0106] Polymerizable compound (C) can be used alone or in combination of two or more types.

[0107] The amount of polymerizable compound (C) is preferably 1 to 50% by mass, and more preferably 2 to 40% by mass, based on 100% by mass of the nonvolatile content of the visible light-shielding photosensitive composition. Adding an appropriate amount further improves curability and developability.

[0108] <Photopolymerization initiator (D)> While various photopolymerization initiators can be used as the photopolymerization initiator (D), in the present invention, oxime ester compounds are preferred.

[0109] (Oxime ester compounds) There are no particular limitations on the oxime ester compounds that can be used in the visible light-shielding photosensitive composition of the present invention, but compounds having a carbazole skeleton are preferably used. This is because they have an absorption wavelength in the range of 330 nm to 430 nm due to the carbazole skeleton, and therefore exhibit high reaction efficiency.

[0110] The photopolymerization initiator (D) is preferably an oxime ester compound having a carbazole skeleton, represented by the following general formula (2).

[0111] General formula (2) [ka] [In general formula (2), X1 to X6 represent a hydrogen atom, a cyclic, linear, or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group. Each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group.]

[0112] Preferred specific examples of oxime ester compounds represented by the above general formula (2) include the following compounds, but the effects of the present invention are not limited to these.

[0113] [ka]

[0114] There are no particular restrictions on the synthesis method of the oxime ester compound represented by formula (2) above, but the following methods can be used. (Step 1) Synthesis of acyl compound The carbazole compound is reacted with an acid chloride in the presence of aluminum chloride to obtain the desired acyl compound. (Step 2) Synthesis of oxime compounds The acyl compound, hydroxylamine hydrochloride, and dimethylformamide are mixed, and this compound is heated and stirred to obtain an oxime compound. (Step 3) Synthesis of the oxime ester compound represented by formula (2) The oxime compound and the acid anhydride are reacted by heating and stirring.

[0115] These oxime ester compounds can be used individually or in any ratio of two or more as needed.

[0116] Other oxime ester compounds 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. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF Japan), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, TR-PBG-358 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Optomer N-1919, ADEKA Arclus NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

[0117] The photopolymerization initiator (D) can be any polymerization initiator other than an oxime ester compound. Other photopolymerization initiators include, for example, 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- Acetophenone compounds such as methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t- Benzophenone compounds such as butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis( Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-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-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples include phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0118] The total content of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the visible light-shielding photosensitive composition. When an appropriate amount is added, the photocurability and developer resistance are improved, and the surface condition of the coating tends to become smoother.

[0119] <Sensitizer (E)> Furthermore, the visible light-shielding photosensitive composition of the present invention may contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0120] Among the sensitizers mentioned above, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are particularly suitable for sensitizing. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc., can be used.

[0121] More specifically, examples of sensitizers include, but are not limited to, those described in "Pigment Handbook" (1986, Kodansha) edited by Shin Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Shin Okawara et al., and "Special Functional Materials" (1986, CMC). In addition, sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included.

[0122] Sensitizers can be used alone or in combination of two or more types.

[0123] The sensitizer content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. Including an appropriate amount further improves curability and developability.

[0124] <Thiol-based chain transfer agent (F)> The visible light-shielding photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerization initiator, thiyl radicals are generated in the radical polymerization process after light irradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive visible light-shielding photosensitive composition.

[0125] Furthermore, the thiol-based chain transfer agent is preferably a polyfunctional aliphatic thiol, which has two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups. More preferably, it is a polyfunctional aliphatic thiol with four or more thiol groups. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0126] Examples of polyfunctional thiols include hexanedithiol and decanedithiol. Examples include 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate are used.

[0127] Thiol-based chain transfer agents can be used alone or in combination of two or more types.

[0128] The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, and more preferably 0.1 to 3% by mass, based on 100% by mass of the nonvolatile content of the visible light-shielding photosensitive composition. When an appropriate amount is included, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating.

[0129] <Polymerization inhibitor (G)> The visible light-shielding photosensitive composition may contain a polymerization inhibitor. This suppresses photosensitivity due to diffracted light from the mask during exposure in photolithography, making it easier to obtain patterns of the desired shape.

[0130] Examples of 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, 2-n- Examples include alkylresorcinol compounds such as butylresorcinol, 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 tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0131] The polymerization inhibitor content is preferably 0.01 to 0.4% by mass of 100% by mass of the nonvolatile content of the visible light-shielding photosensitive composition. Within this range, the effect of the polymerization inhibitor is enhanced, resulting in improved linearity of the taper, wrinkles in the coating film, and pattern resolution.

[0132] <UV absorber (H)> The visible light-shielding photosensitive composition of the invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and examples include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

[0133] The UV absorber content is preferably 5 to 70% by mass of the total 100% by mass of the photopolymerization initiator and UV absorber. Including an appropriate amount further improves resolution after development.

[0134] Furthermore, the total content of the photopolymerization initiator and ultraviolet absorber is preferably 1 to 20% by mass of the nonvolatile content of the visible light-shielding photosensitive composition. Including an appropriate amount further improves the adhesion between the substrate and the film, resulting in good resolution.

[0135] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, a mixture of 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy,C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl Reaction product of 3-(3-(2H-benzotriazole2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl Examples include 4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0136] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction between 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of the resulting compounds include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomeric and polymer-type compounds having a triazine structure can also be used.

[0137] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymeric compounds having a benzophenone structure can also be used.

[0138] Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomeric and polymeric compounds having a salicylic acid ester structure can also be used.

[0139] <Antioxidant (I)> The visible light-shielding photosensitive composition of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the visible light-shielding photosensitive composition from oxidizing and yellowing due to the heat process during heat curing and ITO annealing, thereby improving the transmittance of the coating film. In particular, when the colorant concentration of the visible light-shielding photosensitive composition is high, the amount of coating film crosslinking component decreases, so countermeasures such as using a highly sensitive crosslinking component or increasing the amount of photopolymerization initiator are taken, which can lead to a phenomenon intensifying yellowing during the heat process. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0140] Examples of antioxidants include hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. In this specification, antioxidants that do not contain halogen atoms are preferred.

[0141] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred from the viewpoint of achieving both the transmittance and sensitivity of the coating film.

[0142] Antioxidants can be used alone or in combination of two or more types.

[0143] Furthermore, an antioxidant content of 0.5 to 5.0% by mass per 100% by mass of the nonvolatile content of the visible light-shielding photosensitive composition is more preferable because it results in good transmittance, spectral characteristics, and sensitivity.

[0144] <Leveling agent (J)> In the visible light-shielding photosensitive composition of the present invention, it is preferable to add a leveling agent for the purpose of improving the coatability of the composition on a transparent substrate and the drying properties of the colored film. Various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used as leveling agents.

[0145] 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.

[0146] More specifically, 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, 2110 from Toray Dow Corning Co., Ltd. Examples include 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.

[0147] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0148] More specifically, examples include Surflon S-242, S-243, S-420, S-611, S-651, S-386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 from DIC Corporation, FC-4430, FC-4432 from Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Co., Ltd.

[0149] Nonionic surfactants include 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 tripenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and 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.

[0150] More specifically, Kao Corporation'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, PD450, 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-L1 06, 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 102, 105, Examples include 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic® L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0151] Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0152] More specifically, examples include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0153] 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.

[0154] More specifically, examples include Neos Co., Ltd.'s Futergent 100 and 150, and ADEKA Corporation's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, EC-8600, etc.

[0155] 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.

[0156] More specifically, examples include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0157] When the visible light-shielding photosensitive composition of the present invention contains a surfactant, the amount of surfactant added 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 non-volatile content of the visible light-shielding photosensitive composition of the present invention. Within this range, a good balance is achieved between the coatability, pattern adhesion, and transmittance of the visible light-shielding photosensitive composition. The visible light-shielding photosensitive composition of the present invention may contain only one type of surfactant or two or more types. If two or more types are included, it is preferable that their total amount be within the above range.

[0158] <Storage stabilizer (K)> The visible light-shielding photosensitive composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates. The storage stabilizer can be used in an amount of 0.1 to 10% by mass relative to 100% by mass of the total amount of the colorant.

[0159] <Adhesion enhancer (L)> The visible light-shielding photosensitive composition of the present invention may contain adhesion-enhancing agents such as silane coupling agents to improve adhesion to the substrate. Improved adhesion due to the adhesion-enhancing agent results in better reproduction of fine lines and improved resolution.

[0160] Adhesion enhancers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Examples of silane coupling agents include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant in the visible light-shielding photosensitive composition. This range is preferable because it provides a greater effect and a good balance of adhesion, resolution, and sensitivity.

[0161] <Solvent (M)> The visible light-shielding photosensitive composition of the present invention contains a solvent to facilitate the formation of a colored film by coating it onto a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected considering not only the good coatability of the visible light-shielding photosensitive composition, but also the solubility of each component of the visible light-shielding photosensitive composition, as well as safety.

[0162] As the solvent, solvents commonly used in the field can be used, and their properties such as boiling point, SP value, evaporation rate, and viscosity are taken into consideration, and they are used individually or in mixtures as appropriate according to the application conditions (speed, drying conditions, etc.).

[0163] Examples of solvents that can be used include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0164] Of the above solvents, it is preferable to include an organic solvent whose boiling point at 1 atm is 120°C or higher and 180°C or lower, from the viewpoint of applicability and drying properties. Among these, propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0165] <Method for manufacturing a visible light-shielding photosensitive composition> The visible light-shielding photosensitive composition included in the present invention can be manufactured by finely dispersing a colorant (A) in a colorant carrier such as a resin (B) and / or a solvent, preferably together with a dispersion aid (e.g., a resin-type dispersant, a dye derivative, or a surfactant), using various dispersion methods such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more colorants may be dispersed simultaneously in the colorant carrier, or they may be dispersed separately in the colorant carrier and then mixed. If the colorant, such as a dye, has high solubility, specifically if it has high solubility in the solvent used, dissolves upon stirring, and no foreign matter is detected, then it is not necessary to manufacture it by fine dispersion as described above. Next, a polymerizable compound (C) and a photopolymerization initiator (D), etc., are blended into the colorant dispersion and mixed to obtain a visible light-shielding photosensitive composition. It goes without saying that the timing of blending each material is arbitrary.

[0166] <Removal of coarse particles> The visible light-shielding photosensitive composition of the present invention is preferably subjected to the removal of coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, and any mixed dust by means of centrifugal separation at a gravitational acceleration of 3000 to 25000 G, sintered filters, or membrane filters. Thus, it is preferable that the visible light-shielding photosensitive composition is substantially free of particles of 0.5 μm or larger. More preferably, the particles are 0.3 μm or smaller.

[0167] <Moisture content in visible light-shielding photosensitive composition> In the visible light-shielding photosensitive composition of the present invention, it is preferable that the water content contained in the visible light-shielding photosensitive composition is 2% by mass or less based on 100% by mass of the visible light-shielding photosensitive composition.

[0168] If the water content is within the above range for a visible light-shielding photosensitive composition, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0169] The water content in the visible light-shielding photosensitive composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less, based on 100% by mass of the visible light-shielding photosensitive composition. If the water content is sufficiently low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0170] There are no particular limitations on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing a visible light-shielding photosensitive composition while blowing in a dry inert gas, or adding molecular sieves after manufacturing to dehydrate the composition. Among these, the method of manufacturing while blowing in a dry inert gas is preferred.

[0171] The water content can be measured by known methods such as the Karl Fischer method.

[0172] <Amount of toluene in a visible light-shielding photosensitive composition> The visible light-shielding photosensitive composition of the present invention may contain toluene, and if so, the toluene content is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0173] <Cured film> The cured film of the present invention is formed using the visible light-shielding photosensitive composition described above. The cured film may be used in a laminated state on a substrate, or the cured film may be peeled off from the substrate. The cured film may be a flat film or a film with a pattern, but a film with a pattern is preferred.

[0174] [Method for manufacturing hardened film] The method for manufacturing the cured film is not particularly limited, and known methods can be used. For example, it can be manufactured by a step of coating the visible light-shielding photosensitive composition of the present invention.

[0175] Examples of substrates include those made of materials such as glass, resin, or silicon. An organic light-emitting layer may be formed on these substrates. An image sensor such as a CCD or CMOS may also be formed on the substrate. Furthermore, 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.

[0176] A known coating method can be used. Examples include the drop method, slit coating method, spray method, roll coating method, rotary coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0177] The film thickness can be adjusted as appropriate depending on the purpose. The film thickness is preferably 0.05 to 20.0 μm, more preferably 0.2 to 10.0 μm, and even more preferably 0.3 to 5.0 μm.

[0178] Next, a pattern is formed. Methods for forming the pattern include photolithography and dry etching. Note that when used as a flat film, the pattern formation step is unnecessary; the coating is simply dried as needed.

[0179] The following describes in detail how to form the patterns.

[0180] (When forming a pattern using photolithography) When forming a pattern using photolithography, the visible light-shielding photosensitive composition of the present invention is coated onto a substrate to form a layer. After drying (pre-baking) as necessary, the layer is exposed in a patterned manner through a mask (exposure step). Unexposed areas are removed by alkaline development (development step), and the pattern is then heat-treated as necessary (post-baking step).

[0181] [Exposure process] 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 (for example, at the millisecond level or less) (pulsed exposure).

[0182] [Development process] Next, by performing an alkaline development treatment, the unexposed layers dissolve in the alkaline aqueous solution, leaving only the hardened parts and obtaining 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.

[0183] [Post-baking process] After development, heat treatment (post-baking) can be performed as needed. Post-baking 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 an organic electroluminescent element is used as the light source, the temperature is preferably 150°C or lower, and more preferably 130°C or lower.

[0184] (When forming a pattern using the dry etching method) When forming a pattern by dry etching, for example, a layer formed by coating a substrate with the visible light-shielding photosensitive composition of the present invention is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then dry etching is performed on the cured film using an etching gas, with the patterned photoresist layer as a mask. For pattern formation by dry etching, the method described in Japanese Patent Application Publication No. 2013-064993 can be referenced.

[0185] <Optical filters> The cured film of the present invention can be used in optical filters. The optical filter can be used, for example, as an input means for various image display devices that incorporate a display panel such as a liquid crystal display panel, such as ticket vending machines and ATM devices. The cured film can be used as a component of touch panels, solid-state image sensors, organic EL display devices, etc., and as a component of infrared sensors, such as infrared cut filters and infrared transmission filters.

[0186] <Image display device> As an example of an image display device equipped with the cured film of the present invention, a liquid crystal display device will be described. The liquid crystal display device of the present invention comprises the cured film of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs, but in the present invention, it is preferable to use a white LED because it expands the red color reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the cured film of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged spaced apart and facing each other, with liquid crystal LC sealed between them.

[0187] Liquid crystal (LC) is oriented according to the driving mode, such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on top of it. An alignment layer 14 is provided on top of the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0188] On the other hand, the cured film 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments constituting the cured film 22 are separated by a black matrix (not shown).

[0189] A transparent protective film (not shown) is formed on top of the cured film 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed thereon, and an orientation layer 24 is provided covering the transparent electrode layer 23.

[0190] Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

[0191] White LED light sources include those with a fluorescent filter formed on the surface of a blue LED, and those with a phosphor contained in the resin package of a blue LED. They have a wavelength (λ3) in which the emission intensity is maximum in the range of 430nm to 485nm, a wavelength (λ4) in which the emission intensity is maximum in the range of 530nm to 580nm, and a wavelength (λ5) in which the emission intensity is maximum in the range of 600nm to 650nm, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 (I4 / I3) is between 0.2 and 0.4. Preferably, a white LED light source (LED1) has spectral characteristics in which the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3) is 0.1 or more and 1.3 or less, or a white LED light source (LED2) has spectral characteristics in which the wavelength (λ1) at which the emission intensity is maximum is in the range of 430 nm to 485 nm, the peak wavelength (λ2) of the second emission intensity is in the range of 530 nm to 580 nm, and the ratio of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 (I2 / I1) is 0.2 or more and 0.7 or less.

[0192] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0193] Examples of LED2 include the NSSW440 (manufactured by Nichia Corporation) and the NSSW304D (manufactured by Nichia Corporation).

[0194] <Solid-state image sensor> The cured film of the present invention can be used in solid-state image sensors. The form in which it is used in solid-state image sensors is not particularly limited, but for example, it may have a substrate on which a plurality of photodiodes constituting the light-receiving area of ​​a 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 openings only for the light-receiving portion of the photodiodes is provided on the photodiodes and transfer electrodes, a device protection 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 protection 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 protection film below the filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the filter. The filter may also have a structure in which the cured film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions 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 optical sensors.

[0195] <Infrared sensor> The cured film of the present invention can be used in infrared sensors. The form in which it is used in infrared sensors is not particularly limited. Figure 2 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with the film of the present invention. The infrared sensor shown in Figure 2 comprises a 100 and a solid-state image sensor 110.

[0196] The imaging area provided on the solid-state image sensor 110 is formed by combining an infrared cut filter 111 and a hardened film 112.

[0197] The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400-700 nm) and blocks light in the infrared region.

[0198] The cured film 112 is a cured film in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a cured film in which red (R), green (G), and blue (B) pixels are formed is used.

[0199] Between the infrared transmission filter 113 and the solid-state image sensor 110, a resin film 114 is arranged that allows light of wavelengths transmitted through the infrared transmission filter 113 to pass through. The infrared transmission filter 113 is a filter that blocks light in the visible light region and transmits infrared light of a specific wavelength, and can be formed using the visible light-shielding photosensitive composition of the present invention.

[0200] A microlens 115 is positioned on the incident light h side of the cured film 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0201] In the configuration shown in Figure 2, a resin film 114 is arranged, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0202] This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can also be used as a biometric authentication sensor. [Examples]

[0203] The present invention will be described below with reference to examples. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively. Also, propylene glycol monomethyl acetate may be represented as PGMAc.

[0204] Prior to the examples, the methods for calculating the average molecular weight of the resin and the acid value of the resin will be explained.

[0205] (Average molecular weight of resin) The number-average molecular weight (Mn) and mass-average molecular weight (Mw) of the resin were measured using gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (manufactured by 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 THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a 1 wt% solution of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalents.

[0206] (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 (mgKOH / g) of the resin solution. The acid value per unit solid content of the resin was then calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

[0207] <Method for manufacturing coloring agent (A)> (Coloring agent (A-1)) CI Pigment Blue 15:3 (PB15:3, "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd.) was mixed with 250 parts of sodium chloride and 25 parts of diethylene glycol 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 and then pulverized to obtain coloring agent (A-1) (fine pigment (PB15:3)).

[0208] (Coloring agent (A-2)) Colorant (A-2) (micronized pigment (PB15:4)) was obtained in the same manner as the production of colorant (A-1), except that CI Pigment Blue 15:3 (PB15:3, "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd.) was replaced with CI Pigment Blue 15:4 (PB15:4, "LIONOL BLUE FG-7400G" manufactured by Toyo Color Co., Ltd.).

[0209] (Coloring agent (A-3)) A finely milled pigment (PB15:6) was obtained in the same manner as the production of the coloring agent (A-1), except that CI Pigment Blue 15:3 (PB15:3, "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd.) was replaced with CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd.).

[0210] (Coloring agent (A-4)) Colorant (A-4) (micronized pigment (PY139)) was obtained in the same manner as the production of colorant (A-1), except that CI Pigment Blue 15:3 (PB15:3, "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd.) was replaced with CI Pigment Yellow 139 ("Irgafore Yellow 2R-CF" manufactured by BASF Japan).

[0211] (Coloring agent (A-5)) Colorant (A-5) (micronized pigment (PY185)) was obtained in the same manner as the production of colorant (A-1), except that CI Pigment Blue 15:3 (PB15:3, "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd.) was replaced with CI Pigment Yellow 185 ("Paliotol Yellow L 1155" manufactured by BASF Japan).

[0212] (Manufacturing of coloring agent (A-6)) Colorant (A-6) (micronized pigment (PV23)) was obtained in the same manner as the production of colorant (A-1), except that CI Pigment Blue 15:3 (PB15:3, "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd.) was replaced with CI Pigment Violet 23 ("Lionogen Violet RL" manufactured by Toyo Color Co., Ltd.).

[0213] <Dye derivative (a)> The following basic pigment derivatives were used. Dye derivative (a-1) [ka] Dye derivative (a-2) [ka] Dye derivative (a-3) [ka] Dye derivative (a-4) [ka]

[0214] <Production of resin (B1) having aromatic carboxylic acid moieties and vinyl polymer moieties> (Preparation of resin (B1-1-1) solution containing aromatic carboxylic acid moieties and (meth)acryloyl group-containing vinyl polymer moieties) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 8 parts of 3-mercapto-1,2-propanediol, 12 parts of pyromellitic anhydride, 80 parts of propylene glycol monomethyl ether acetate, 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 had been half-esterified. Next, 15 parts of methyl methacrylate, 5 parts of methacrylic acid, 30 parts of 2-methoxyethyl acrylate, 20 parts of t-butyl methacrylate, and 30 parts of 2-hydroxyethyl methacrylate were charged, the reaction vessel was heated to 80°C, and 1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours (second step). Next, the flask was purged with air, and 54.0 parts of 2-methacryloyloxyethyl isocyanate and 0.1 parts of hydroquinone were added, and the reaction was carried out at 70°C for 4 hours (third step). After confirming the disappearance of the 2270 cm-1 peak based on the isocyanate group by IR, the reaction solution was cooled, and the non-volatile content was adjusted with propylene glycol monomethyl ether acetate to obtain a resin solution (B1-1-1) with a non-volatile content of 40%, an acid value of 70, and a weight-average molecular weight of 12,000.

[0215] (Preparation of resin solutions (B1-1-2) to (B1-1-4) containing aromatic carboxylic acid moieties and (meth)acryloyl group-containing vinyl polymer moieties) The resins (B1-1-2) to (B1-1-4) were synthesized in the same manner as the production of resin (B1-1-1), except that the raw materials and preparation amounts listed in Table 1 were used, and solutions of resins (B1-1-2) to (B1-1-4) with a non-volatile content of 40% were obtained.

[0216] [Table 1]

[0217] The abbreviations used in Table 1 are as follows: PGMAc: Propylene glycol monomethyl ether acetate MMA: Methyl methacrylate MAA: Methacrylic acid t-BMA: t-butyl methacrylate t-BA:t-butyl acrylate EA: Ethyl acrylate HEMA: 2-hydroxyethyl methacrylate MOI: 2-Methacryloyloxyethyl isocyanate (Showa Denko Corporation: Karenz MOI) AOI: 2-Acryloyloxyethyl isocyanate (manufactured by Showa Denko Corporation: Karenz AOI)

[0218] (Preparation of a resin (B1-2-1) solution containing aromatic carboxylic acid moieties and vinyl polymer moieties that do not contain (meth)acryloyl groups) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 45.0 parts methyl methacrylate, 5.0 parts methacrylic acid, and 50.0 parts t-butyl acrylate were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 6.0 parts 3-mercapto-1,2-propanediol and 0.1 parts 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 70.7 parts propylene glycol monomethyl ether acetate was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that more than 95% of the monomers had reacted. Next, 14.5 parts of pyromellitic dianhydride, 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. By measuring the amount of remaining acid anhydride, it was confirmed that 80% of the acid anhydride had reacted. Subsequently, 12.1 parts of 3-methoxybutanol were added, and the mixture was reacted at 120°C for 3 hours to form a encapsulation site. The acid value was measured to confirm that more than 98% of the acid anhydride had reacted, and the reaction was terminated. Then, by adjusting the non-volatile content with propylene glycol monomethyl ether acetate, a solution of resin (B1-2-1) with a non-volatile content of 40%, an acid value of 110 mgKOH / g, and a weight-average molecular weight of 9000 was obtained.

[0219] (Preparation of resins (B1-2-2), (B1-2-3), (B1-3-1), and (B1-3-2) solutions containing aromatic carboxylic acid moieties and vinyl polymer moieties that do not contain (meth)acryloyl groups) The resins were synthesized in the same manner as the resin (B1-2-1), except that the raw materials and amounts used were as listed in Table 2, and solutions of resins (B1-2-2), (B1-2-3), (B1-3-1), and (B1-3-2) with a non-volatile content of 40% were obtained.

[0220] [Table 2]

[0221] The abbreviations used in Table 2 are as follows: PGMAc: Propylene glycol monomethyl ether acetate MMA: Methyl methacrylate MAA: Methacrylic acid t-BA:t-butyl acrylate EA: Ethyl acrylate

[0222] (Production of resin (B2-1) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 17.9 parts of 1-dodecanol, 82.1 parts of ε-caprolactone, and 0.03 parts of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was heated and stirred at 120°C for 4 hours. After confirming that more than 98% of the monomers had reacted by measuring the non-volatile content, 20.9 parts of pyromellitic dianhydride were added and the mixture was reacted at 120°C for 2 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. A resin (B2-1) solution with a non-volatile content of 20% was obtained by adjusting the non-volatile content with propylene glycol monomethyl ether acetate. The obtained dispersant was a white solid at room temperature and had an acid value of 51 mgKOH / g.

[0223] (Production of resin (B2-2) 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. 196 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 45 parts n-butyl methacrylate, 15 parts 2-hydroxyethyl methacrylate, 15 parts methacrylic acid, 25 parts paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 3 hours to obtain an acrylic resin solution. 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 non-volatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution to achieve a non-volatile content of 20% to prepare resin (B2-2) solution. The weight-average molecular weight (Mw) was 26,000.

[0224] (Production of resin (B2-3) solution) 370 parts of cyclohexanone were placed in a separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. The temperature was raised to 80°C, and the flask was purged with nitrogen. Then, a mixture of 25 parts of paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 15 parts of benzyl methacrylate, 25 parts of glycidyl methacrylate, 35 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise over 2 hours via the dropping tube. After the dropwise addition, the mixture was reacted at 100°C for 3 hours, and then 1.0 part of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for another hour. Next, the container was replaced with an air-purging system, and 9.3 parts of acrylic acid (equivalent to 100 mol% of 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 non-volatile acid value reached 0.5, at which point the reaction was terminated to obtain a resin solution. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (equivalent to 100 mol% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and the mixture was reacted at 120°C for 3.5 hours to obtain another 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 non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to prepare resin (B2-3) solution so that the non-volatile content was 20% by mass. The weight-average molecular weight (Mw) was 19000.

[0225] <Method for producing colored composition> [Manufacturing Example 1] (Preparation of colored composition (R-1)) After stirring and mixing the following mixture until homogeneous, it was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 5.0 μm pore size filter to prepare a colored composition (R-1) with 26% by mass of nonvolatile components. (R-1) Coloring agent (A-1): 20.0 parts Resin (B) solution (B1-1-1, 40% non-volatile content solution): 15.0 parts Solvent (PGMAc): 65.0 parts

[0226] (R-2 to R-15)) As shown in Table 3, except for changing the types and amounts of each material, the colored compositions (R-2 to R-15) were prepared in the same manner as the above-described colored composition (R-1).

[0227] [Table 3]

[0228] [Method for manufacturing visible light-shielding photosensitive composition] [Example 1] [Preparation of visible light-shielding photosensitive composition (X-1)] The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a visible light-shielding photosensitive composition (X-1). Colored composition 1 (R-1: 26% non-volatile content): 22.0 parts Colored composition 2 (R-14: 26% non-volatile content): 22.0 parts Colored composition 3 (R-15: 26% non-volatile content): 10.0 parts Resin (B1) solution (B1-2-1, 40% non-volatile content): 10.0 parts Polymerizable compound (C) (C-1): 2.0 parts Photoinitiator (D) (D-1): 0.3 parts Sensitizer (E): 0.2 parts Thiol-based chain transfer agent (F): 0.4 parts Polymerization inhibitor (G): 0.1 part Ultraviolet absorber (H): 0.1 part Antioxidant (I): 0.1 part Leveling agent (J: 3% non-volatile content): 1.0 part Storage stabilizer (K): 0.1 part Adhesion improver (L): 0.2 part Solvent (M): 31.5 parts

[0229] [Examples 2-37, Comparative Examples 1-8] (Preparation of visible light-shielding photosensitive compositions (X-2~45)) Except for changing the types and mass parts of the colored composition, resin (B1) solution, resin (B2) solution, polymerizable compound (C), photopolymerization initiator (D), and solvent (M) from Example 1 as shown in Tables 4-1 and 4-2, visible light-shielding photosensitive compositions (X2-45) were prepared in the same manner as in Example 1.

[0230] [Table 4-1]

[0231] [Table 4-2]

[0232] The ingredients for each product are as follows:

[0233] <Polymerizable compound (C)> (C-1) Ethylene oxide 12 molar modified dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) (number of repeating ethyleneoxy units = 2)] (C-2) Ethylene oxide 6 molar modified trimethylolpropane triacrylate [Arronix M-306 (manufactured by Toagosei Co., Ltd.) (number of repeating ethyleneoxy units = 2)] (C-3) Ethylene oxide 4 molar modified pentaerythritol tetraacrylate [KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) (number of repeating ethylene oxy groups = 4)] (C-4) Ethylene oxide 4 molar modified diglycerin tetraacrylate [Arronix M-460 (manufactured by Toagosei Co., Ltd.) (number of repeating ethylene oxy groups = 1)] (C-5) Ethylene oxide 3 molar modified trimethylolpropane triacrylate [Arronix M-350 (manufactured by Toagosei Co., Ltd.) (number of repeating ethyleneoxy units = 1)] (C-6) Dipentaerythritol Penta and Hexaacrylate [Aronix M-402 (manufactured by Toagosei Co., Ltd.) (number of repeating units of ethyleneoxy group = 0)] (C-7) Trimethylolpropane Triacrylate [Aronix M-309 (manufactured by Toagosei Co., Ltd.) (number of repeating units of ethyleneoxy group = 0)]

[0234] <Photoinitiator (D)> (D-1) The following structure [Irgacure OXE02 (manufactured by BASF)]

Chemical formula

Chemical formula

Chemical formula

[0235] <Thiol-based chain transfer agent (F)> (F-1) Trimethylolethane Tris(3-mercaptobutyrate) [TEMB (manufactured by Showa Denko K.K.)] (F-2) Trimethylolpropane Tris(3-mercaptobutyrate) [TPMB (manufactured by Showa Denko K.K.)] (F-3) Pentaerythritol Tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (F-4) Trimethylolpropanetris (3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (F-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (F-1) to (F-5) were mixed in equal amounts to form the thiol-based chain transfer agent (F).

[0236] <Polymerization inhibitor (G)> (G-1)3-methylcatechol (G-2) Methylhydroquinone (G-3) tert-butylhydroquinone The above (G-1) to (G-3) were mixed in equal amounts to form polymerization inhibitor (G).

[0237] <UV absorber (H)> (H-1)2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN400 (manufactured by BASF Japan)] (H-2)2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)] As described above, (H-1) and (H-2) were mixed in equal amounts to obtain the ultraviolet absorber (H).

[0238] <Antioxidant (I)> (I-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (I-2)3,3'-Dioctadecyl Thiodipropanoate (I-3) Tris[2,4-di-(tert)-butylphenyl]phosphine (I-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (I-5) p-octylphenyl salicylate The above (I-1) to (I-5) were mixed in equal amounts to form antioxidant (I).

[0239] <Leveling agent (J)> One unit of "BYK-330" manufactured by Big Chemie Co., Ltd. One copy of DIC's "Megafuck F-551". Kao Corporation's "Emulgen 103" (1 unit) The above was dissolved in 97 parts of PGMAc to create a mixed solution which was used as the leveling agent (J).

[0240] <Storage stabilizer (K)> (K-1)2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT manufactured by Honshu Chemical Industry Co., Ltd.) (K-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.) As described above, (K-1) and (K-2) were mixed in equal amounts to form storage stabilizer (K).

[0241] <Adhesion enhancer (L)> (L-1)3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (L-2)3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (L-3)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (L-4)3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (L-1) to (L-4) were mixed in equal amounts to form the silane coupling agent (L).

[0242] <Solvent (M)> (M-1) PGMAc 30 copies (M-2) Cyclohexanone 30 parts (M-3)3-Ethoxypropionate 10 parts (M-4) Propylene glycol monomethyl ether 10 parts (M-5) Cyclohexanol acetate 10 parts (M-6) Dipropylene glycol methyl ether acetate 10 parts The above (M-1) to (M-6) were mixed in the above-mentioned parts by mass to obtain solvent (M).

[0243] <Evaluation of visible light-blocking photosensitive compositions> The obtained visible light-shielding photosensitive compositions were evaluated for visible light shielding, alkali developability, and resolution as follows. ◎ indicates a very good level, ○ indicates a good level, △ indicates a usable level, and × indicates a level unsuitable for practical use.

[0244] (Evaluation of visible light shielding properties) The obtained visible light-shielding photosensitive composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, and the substrate was prepared by baking it in an oven at 230°C for 30 minutes to obtain a coating thickness of 1.0 μm after heat treatment. The obtained coated substrates were subjected to a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100") to measure the transmittance in the thickness direction, and the visible light shielding properties were evaluated by measuring the maximum transmittance in the 400-700 nm region. ◎: Maximum light transmittance is less than 3.0% ○: Maximum transmittance is 3.0% or more, and less than 5.0%. △: Maximum transmittance is 5.0% or more, but less than 7.0%. ×: Maximum light transmittance is 7.0% or higher

[0245] (Evaluation of alkaline developability) On a 6-inch silicon wafer, a resist solution for planarization (HL-18s, manufactured by Nippon Steel Chemical Co., Ltd.) was applied by spin coating. After heating on a 100°C hot plate for 6 minutes, the coating was cured by heating in a 230°C oven for 1 hour to obtain a silicon wafer with a planarized film. Next, the coloring compositions (R-1, R-31~49) were each applied to the planarized film by spin coating to a dry film thickness of 0.7 μm. The mixture was pre-baked on a 100°C hot plate for 1 minute, and then exposed to a photomask using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon) at a wavelength of 365 nm to form 1.0 μm square pixels, with an exposure dose of 3000 J / m². 2 Pattern exposure was performed. After exposure, the coating film was paddle-developed with an organic alkaline developer. After paddle development, the wafer was washed with pure water using a 20-second spin shower, any remaining water droplets were blown off with high-pressure air, and the substrate was allowed to air dry to form a square pixel pattern. The surface of the unexposed areas washed away by development was observed with a scanning electron microscope (Hitachi High-Tech Corporation "S-3000N"), and the alkali developability was determined by the presence or absence of residue. ◎: No residue after 1 minute of development time. ○: A small amount of residue is visible after a development time of 1 minute. △: Some residue is visible after a development time of 1 minute. ×: A large amount of residue is visible even with a development time of 1 minute.

[0246] (Adhesion) A test substrate was formed using the same procedure as in the alkali developability test described above, and the percentage of missing pixels among 50 pattern pixels with a diameter of 1.0 μm square was observed using a scanning electron microscope (Hitachi High-Tech Corporation's "S-3000N"). ◎: No missing pixels among the 50 pattern pixels. ○: Out of 50 pattern pixels, there are 1 to less than 3 missing pixels. △: Out of 50 pattern pixels, 3 to 6 pixels are missing. ×: Out of 50 pattern pixels, 6 or more pixels are missing but less than 10.

[0247] The results of the evaluation using the above method are shown in Table 5. [Table 5]

[0248] As shown in Table 5, the visible light-shielding photosensitive compositions of Examples 1 to 37 exhibited excellent light-shielding properties in the visible light region of 400 to 700 nm wavelengths, and enabled the formation of cured films that combined alkali developability and pattern adhesion. [Explanation of Symbols]

[0249] 10 LCD display device 11 Transparent substrate 12 TFT arrays 13 Transparent electrode layer 14. Orientation layer 15 Polarizing plates 21 Transparent substrate 22 Color Filters 23 Transparent electrode layer 24 orientation layer 25 Polarizing plates 30 backlight units 31 White LED light source LC LCD 100 Infrared Sensors 110 Photodetector 111 Infrared Absorption Filter 112 Color Filters 113 Infrared Absorption and Transmission Filter 114 Resin film 115 Microlenses 116 Flat membrane

Claims

1. A visible light-shielding photosensitive composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The content of the coloring agent (A) is 50% by mass or more of the total solid content of the visible light-shielding photosensitive composition. The coloring agent (A) contains, in 100% by mass of coloring agent (A), 20 to 50% by mass of copper phthalocyanine blue pigment, 20 to 50% by mass of C.I. Pigment Yellow 139, and 15 to 45% by mass of C.I. Pigment Violet 23. The resin (B) comprises a resin (B1) having an aromatic carboxylic acid moiety and a vinyl polymer moiety. The content of the resin (B1) is 80% by mass or more of 100% by mass of the resin (B), A visible light-shielding photosensitive composition characterized in that the polymerizable compound (C) contains a polymerizable compound (C1) having a chain with two or more repeating ethyleneoxy groups.

2. The visible light-shielding photosensitive composition according to claim 1, wherein the copper phthalocyanine blue pigment is one or more selected from the group consisting of C.I. Pigment Blue 15:3, 15:4, and 15:

6.

3. The resin (B1) includes a resin (B1-1) containing a (meth)acryloyl group-containing vinyl polymer moiety. The visible light-shielding photosensitive composition according to claim 1 or 2, characterized in that the content of the resin (B1-1) is 50% by mass or more of the total solid content of the resin (B1).

4. The resin (B1) includes a resin (B1-2) that does not contain a (meth)acryloyl group-containing vinyl polymer moiety. The visible light-shielding photosensitive composition according to claim 1 or 2, characterized in that the acid value of the resin (B1-2) is 100 mg KOH / g or more.

5. The visible light-shielding photosensitive composition according to claim 1 or 2, wherein the photopolymerization initiator (D) comprises a compound represented by the following general formula (1). General formula (1) 【Chemistry 1】 [In general formula (1), X １ ~X ６ This represents a hydrogen atom, a cyclic, linear, or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group.

6. A cured film produced using the visible light-shielding photosensitive composition described in claim 1 or 2.

7. An optical filter having the cured film described in claim 6.

8. An image display device having the cured film according to claim 6.

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

10. An infrared sensor having a cured film as described in claim 6.

Images