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

Abstract

Provided are: a photosensitive composition comprising: a pigment-containing coloring agent A, a pigment derivative B, and a resin C, wherein the coloring agent A contains a blue pigment, and the pigment derivative B contains a transparent pigment derivative B1 and a chromatic pigment derivative B2, the total content of the coloring agent A and the pigment derivative B in the total solid content of the photosensitive composition is 40 mass% or more; a film using the photosensitive composition; a color filter; a solid imaging element; and an image display device.

Description

[Technical Field]

[0001] This invention relates to a photosensitive composition containing a blue pigment. Furthermore, this invention relates to a film, a color filter, a solid-state image sensor, and an image display device using the photosensitive composition. [Background technology]

[0002] In recent years, the demand for solid-state image sensors, such as charge-coupled (CCD) image sensors, has grown significantly due to the widespread use of digital cameras and camera-equipped mobile phones. Color filters are used as key devices in displays and optical elements.

[0003] Color filters are manufactured using a photosensitive composition containing a coloring agent. Generally, when a pigment is used as the coloring agent, the pigment is dispersed in the photosensitive composition using pigment derivatives or resins.

[0004] Patent Document 1 describes an invention relating to a photosensitive composition comprising a pigment, a predetermined dye derivative having a triazine structure, a predetermined resin-type dispersant, a polymerizable monomer, a photopolymerization initiator, a resin binder, and a solvent. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-133154 [Overview of the project] [Problems that the invention aims to solve]

[0006] Films obtained using photosensitive compositions containing blue pigments tended to discolor easily upon light exposure. In recent years, there has been a demand for further improvement in lightfastness of films used in color filters and the like, and further improvement in lightfastness is also desired for films obtained using photosensitive compositions containing blue pigments.

[0007] Furthermore, in recent years, there has been a growing demand for improved moisture resistance in films used in color filters and other applications.

[0008] Therefore, an object of the present invention is to provide a photosensitive composition that can form a film with excellent light resistance and moisture resistance. Furthermore, the present invention is to provide a film, a color filter, a solid-state image sensor, and an image display device. [Means for solving the problem]

[0009] Through the inventors' research, it was discovered that the above objective can be achieved by the following configuration, and thus the present invention was completed. Therefore, the present invention provides the following. <1> A photosensitive composition comprising a colorant A containing a pigment, a pigment derivative B, and a resin C, The above coloring agent A contains a blue pigment. The above-mentioned pigment derivative B includes a transparent pigment derivative B1 and a chromatic pigment derivative B2. A photosensitive composition wherein the total content of the colorant A and the pigment derivative B in the total solid content of the photosensitive composition is 40% by mass or more. <2> The maximum molar extinction coefficient of the above pigment derivative B1 in the wavelength range of 400-700 nm is 3000 L·mol. -1 ·cm -1 The following is: <1> The photosensitive composition described in [reference]. <3> The maximum molar extinction coefficient of the above pigment derivative B2 in the wavelength range of 400-700 nm is 10,000 L·mol. -1 ·cm -1 That's all. <1> or <2> The photosensitive composition described in [reference]. <4> The above pigment derivative B1 is a compound having a triazine ring. <1> ~ <3> A photosensitive composition as described in any one of the following. <5> The above pigment derivative B1 is a compound containing a group represented by formula (A1). <1> ~ <4> A photosensitive composition according to any one of the following; [ka] In formula (A1), * represents a bond, Ya 1 and Ya 2 each independently represents -N(Ra 1 )- or -O-, Ra 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, B 1 and B 2 each independently represents a hydrogen atom or a substituent. <6> The photosensitive composition according to any one of <1> to <5>, wherein the pigment derivative B2 is a phthalocyanine compound. <7> The photosensitive composition according to any one of <1> to <6>, wherein the maximum absorption wavelength of the pigment derivative B2 is in the range of 400 to 700 nm. <8> The photosensitive composition according to any one of <1> to <7>, wherein the blue pigment is a phthalocyanine compound. <9> The photosensitive composition according to any one of <1> to <8>, wherein the colorant A contains a blue pigment and a purple pigment. <10> The photosensitive composition according to any one of <1> to <9>, further comprising a polymerizable monomer and a photoinitiator. <11> When a film with a thickness of 1 μm is formed using the photosensitive composition, the average value of the light transmittance in the wavelength range of 400 to 500 nm in the thickness direction of the film is 55% or more, and the average value of the light transmittance in the wavelength range of 600 to 700 nm in the thickness direction of the film is 20% or less, and the wavelength at which the transmittance shows 50% is in the range of 450 to 550 nm. The photosensitive composition according to any one of <1> to <10>. <12> The photosensitive composition according to any one of <1> to <11>, which is a photosensitive composition for forming a blue pixel. <13> A film obtained from the photosensitive composition according to any one of <1> to <12>. <14> A color filter having the film according to <13>. <15> A solid-state imaging device having the film according to <13>. <16> An image display device having the film according to <13>. [Effects of the Invention]

[0010] The present invention can provide a photosensitive composition, film, color filter, solid-state image sensor, and image display device that can form a film with excellent light resistance and moisture resistance. [Modes for carrying out the invention]

[0011] The details of the present invention will be described in detail below. In this specification, "~" is used to mean that the numbers before and after it include the lower and upper limits, respectively. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, symbols preceding or following names (e.g., A, B, and C) are terms used to distinguish components and do not limit the types, number, or hierarchy of components. In this specification, the weight-average molecular weight and number-average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography). In this specification, total solids refers to the total mass of the components of the composition excluding the solvent. In this specification, "pigment" means a coloring agent that is poorly soluble in a solvent. For example, the pigment preferably has a solubility of 0.1 g or less, and more preferably 0.01 g or less, in 100 g of water at 23°C and 100 g of propylene glycol monomethyl ether acetate at 23°C. In this specification, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended function is achieved.

[0012] <Photosensitive composition> The photosensitive composition of the present invention is a photosensitive composition comprising a colorant A containing a pigment, a pigment derivative B, and a resin C, Colorant A contains blue pigment, Pigment derivative B includes a transparent pigment derivative B1 and a chromatic pigment derivative B2. The photosensitive composition is characterized in that the total content of colorant A and pigment derivative B in the total solid content is 40% by mass or more.

[0013] The photosensitive composition of the present invention can form a film with excellent light resistance and moisture resistance. The reason for these effects is presumed to be as follows: The photosensitive composition of the present invention contains a transparent pigment derivative B1. Therefore, when forming a photosensitive composition layer on a support using the photosensitive composition and curing this photosensitive composition layer by exposure, it is presumed that exposure makes it easier to transmit light to the deeper parts (support side) of the photosensitive composition layer. For this reason, it is presumed that a sufficiently cured film can be formed by exposure. Furthermore, since the photosensitive composition of the present invention contains a chromatic pigment derivative B2 in addition to the transparent pigment derivative B1, it is presumed that even if the film after film formation is irradiated with light, this pigment derivative B2 will absorb the light appropriately, suppressing the decomposition and modification of resins, colorants, etc. For this reason, it is presumed that a film with excellent light resistance can be formed by using the photosensitive composition of the present invention. Furthermore, since the photosensitive composition of the present invention contains a transparent pigment derivative B1 in addition to the chromatic pigment derivative B2, even if a film formed using the photosensitive composition is exposed to a high-humidity environment and decomposition or modification of the pigment derivative occurs, the effect of spectral fluctuations due to the decomposition or modification of the pigment derivative can be reduced, and it is presumed that a film with excellent moisture resistance can be formed.

[0014] Furthermore, the photosensitive composition of the present invention also exhibits excellent storage stability. Since the photosensitive composition of the present invention contains two or more pigment derivatives, it is presumed that a pigment-pigment derivative-resin network is easily formed within the photosensitive composition, thereby suppressing pigment aggregation, and as a result, the storage stability of the photosensitive composition has been improved.

[0015] The blue hue is a highly transmittance hue with a wavelength of around 400-500 nm, and is a hue that is extremely susceptible to spectral effects due to yellowing of resins and other materials. Since the film formed by the photosensitive composition of the present invention can suppress yellowing due to light irradiation, the photosensitive composition of the present invention can be preferably used as a photosensitive composition for forming blue pixels.

[0016] The photosensitive composition of the present invention is preferably used as a photosensitive composition for color filters. Specifically, it is preferably used as a photosensitive composition for forming blue pixels in color filters.

[0017] When a film with a thickness of 1 μm is formed using the photosensitive composition of the present invention, it is preferable that the average transmittance of light in the wavelength range of 400 to 500 nm in the thickness direction of the film is 55% or more, the average transmittance of light in the wavelength range of 600 to 700 nm in the thickness direction of the film is 20% or less, and that the wavelength at which the transmittance is 50% exists in the wavelength range of 450 to 550 nm. A photosensitive composition that satisfies such spectral characteristics can be preferably used as a photosensitive composition for forming blue pixels. The average transmittance of the above film in the wavelength range of 400 to 500 nm is preferably 60% or higher, and more preferably 70% or higher. The average transmittance of the above film in the wavelength range of 600 to 700 nm is preferably 15% or less, and more preferably 10% or less. The wavelength at which the above film exhibits a transmittance of 50% is preferably in the range of 460 to 540 nm, and more preferably in the range of 470 to 520 nm.

[0018] The solid content concentration of the photosensitive composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0019] The following describes each component used in the photosensitive composition of the present invention.

[0020] <<Coloring agent A>> The photosensitive composition of the present invention contains a colorant A (hereinafter also referred to as the colorant). In the present invention, a colorant containing a pigment is used.

[0021] The pigment content in the colorant contained in the photosensitive composition is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and even more preferably 40 to 100% by mass. It is also preferable that the colorant contained in the photosensitive composition consists substantially only of pigment. When the colorant contained in the photosensitive composition consists substantially only of pigment, it means that the pigment content in the colorant is 99% by mass or more, preferably 99.9% by mass or more, and even more preferably consisting only of pigment. The colorant contained in the photosensitive composition may include both a pigment and a dye. When both a pigment and a dye are used, the amount of dye is preferably 2 to 300 parts by mass per 100 parts by mass of blue pigment. The upper limit is preferably 200 parts by mass or less, and more preferably 100 parts by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.

[0022] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. If the average primary particle diameter of the pigment is within the above range, the dispersibility of the pigment in the photosensitive composition is good. The primary particle diameter of the pigment can be determined by observing the primary particles of the pigment with a transmission electron microscope and obtaining a photograph. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding equivalent circle diameter is calculated as the primary particle diameter of the pigment. In this specification, the average primary particle diameter of the pigment is the arithmetic mean of the primary particle diameters of 400 primary particles of the pigment. Furthermore, primary particles of the pigment refer to independent particles that are not aggregated. The crystallite size, determined from the full width at half maximum of the peaks originating from any crystal plane in the X-ray diffraction spectrum when the CuKα rays of the pigment are used as the X-ray source, is preferably 0.1 nm to 100 nm, more preferably 0.5 nm to 50 nm, even more preferably 1 nm to 30 nm, and particularly preferably 5 nm to 25 nm.

[0023] The colorant contained in the photosensitive composition of the present invention includes a blue pigment. Examples of blue pigments include phthalocyanine pigments and triarylmethane pigments, with phthalocyanine pigments being preferred. Specific examples of blue pigments include color index (CI) pigment blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. In addition, aluminum phthalocyanine pigments having phosphorus atoms can also be used as blue pigments. Specific examples include the compounds described in paragraphs 0022 to 0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.

[0024] The content of blue pigment in the colorant contained in the photosensitive composition is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit may be 100% by mass or less, 80% by mass or less, or 60% by mass or less.

[0025] The coloring agent preferably further contains a purple pigment. That is, the coloring agent preferably contains both a blue pigment and a purple pigment. According to this embodiment, it is easy to form a film with a hue suitable for blue spectral dispersion. Furthermore, conventionally, when blue pigment and purple pigment were used in combination, the spectral characteristics derived from the purple pigment tended to fluctuate easily upon light irradiation. However, according to the photosensitive composition of the present invention, even when blue pigment and purple pigment are used in combination, fluctuations in spectral characteristics due to light irradiation can be suppressed, and a film with excellent light resistance can be formed.

[0026] Examples of purple pigments include xanthene pigments, quinacridone pigments, dioxazine pigments, and benzimidazolone pigments, with xanthene pigments and dioxazine pigments being preferred. Specific examples of purple pigments include CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0027] The purple pigment content is preferably 2 to 100 parts by mass per 100 parts by mass of blue pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more. Furthermore, the total content of blue pigment and purple pigment in the colorant contained in the photosensitive composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more. The upper limit may be 100% by mass or less, 90% by mass or less, or 80% by mass or less. The colorants contained in the photosensitive composition are preferably substantially composed of only blue pigment and purple pigment. When the colorants contained in the photosensitive composition are substantially composed of only blue pigment and purple pigment, it means that the total content of blue pigment and purple pigment in the colorants is 99% by mass or more, preferably 99.9% by mass or more, and even more preferably only pigments.

[0028] The coloring agent may further contain pigments of hues other than blue and purple pigments (hereinafter also referred to as "other pigments"). Examples of other pigments include yellow pigment, orange pigment, red pigment, and green pigment. Specific examples of these include the following:

[0029] CIPigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63, 65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,12 6, 127, 128, 129, 137, 138, 139, 147, 148, 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, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 etc. (all yellow pigments), CIPigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (all are orange pigments) CIPigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53: 1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297 etc. (all red pigments), CIPigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66, etc. (all are green pigments).

[0030] Furthermore, as a green pigment, zinc halide phthalocyanine pigments can be used, which have an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule. A specific example is the compound described in International Publication No. 2015 / 118720. In addition, as a green pigment, compounds described in Chinese Patent Application No. 106909027, phthalocyanine compounds having a phosphate ester as a ligand as described in International Publication No. 2012 / 102395, phthalocyanine compounds described in Japanese Patent Publication No. 2019-008014, phthalocyanine compounds described in Japanese Patent Publication No. 2018-180023, compounds described in Japanese Patent Publication No. 2019-038958, aluminum phthalocyanine compounds described in Japanese Patent Publication No. 2020-070426, and core-shell type dyes described in Japanese Patent Publication No. 2020-076995 can also be used.

[0031] Furthermore, a nickel azobarbiturate complex with the following structure can also be used as a yellow pigment. [ka]

[0032] Furthermore, as a yellow pigment, the compounds described in Japanese Patent Publication No. 2017-201003, Japanese Patent Publication No. 2017-197719, Japanese Patent Publication No. 2017-171912 (paragraphs 0011-0062, 0137-0276), Japanese Patent Publication No. 2017-171913 (paragraphs 0010-0062, 0138-0295), Japanese Patent Publication No. 2017-171914 (paragraphs 0011-0062, 0139-0190), and Japanese Patent Publication No. 2017-171915 (paragraphs 0010-0065, 0142-0222) The following are examples of the following compounds: quinophthalone compounds described in paragraphs 0011-0034 of JP 2013-054339, quinophthalone compounds described in paragraphs 0013-0058 of JP 2014-026228, isoindoline compounds described in JP 2018-062644, quinophthalone compounds described in JP 2018-203798, quinophthalone compounds described in JP 2018-062578, quinophthalone compounds described in Japanese Patent No. 6432076, quinophthalone compounds described in JP 2018-155881, and JP 2018-1117 Quinophthalone compounds described in Japanese Patent Publication No. 57, Quinophthalone compounds described in Japanese Patent Publication No. 2018-040835, Quinophthalone compounds described in Japanese Patent Publication No. 2017-197640, Quinophthalone compounds described in Japanese Patent Publication No. 2016-145282, Quinophthalone compounds described in Japanese Patent Publication No. 2014-085565, Quinophthalone compounds described in Japanese Patent Publication No. 2014-021139, Quinophthalone compounds described in Japanese Patent Publication No. 2013-209614, Quinophthalone compounds described in Japanese Patent Publication No. 2013-209435, Quinophthalone compounds described in Japanese Patent Publication No. 2013-181015 Quinophthalone compounds, quinophthalone compounds described in Japanese Patent Publication No. 2013-061622, quinophthalone compounds described in Japanese Patent Publication No. 2013-032486, quinophthalone compounds described in Japanese Patent Publication No. 2012-226110, quinophthalone compounds described in Japanese Patent Publication No. 2008-074987, quinophthalone compounds described in Japanese Patent Publication No. 2008-081565, quinophthalone compounds described in Japanese Patent Publication No. 2008-074986, quinophthalone compounds described in Japanese Patent Publication No. 2008-074985, quinophthalone compounds described in Japanese Patent Publication No. 2008-050420,Quinophthalone compounds described in Japanese Patent Publication No. 2008-031281, Quinophthalone compounds described in Japanese Patent Publication No. 48-032765, Quinophthalone compounds described in Japanese Patent Publication No. 2019-008014, Quinophthalone compounds described in Japanese Patent Publication No. 6607427, Compounds described in Korean Published Patent No. 10-2014-0034963, Compounds described in Japanese Patent Publication No. 2017-095706, Compounds described in Taiwan Patent Application Publication No. 201920495, Compounds described in Japanese Patent Publication No. 6607427, Compounds described in Japanese Patent Publication No. 2020-033525, Compounds described in Japanese Patent Publication No. 2020-033524 Compounds described in Japanese Patent Publication No. 2020-033523, Japanese Patent Publication No. 2020-033522, Japanese Patent Publication No. 2020-033521, International Publication No. 2020 / 045200, International Publication No. 2020 / 045199, International Publication No. 2020 / 045197, azo compounds described in Japanese Patent Publication No. 2020-093994, perylene compounds described in Japanese Patent Publication No. 2020-083982, perylene compounds described in International Publication No. 2020 / 105346, and quinophthalone compounds described in Japanese Patent Publication No. 2020-517791 can also be used.

[0033] As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in Japanese Patent Publication No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016-0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, brominated diketopyrrolopyrrole compounds described in Japanese Patent Publication No. 2020-085947, naphthol azo compounds described in Japanese Patent Publication No. 2012-229344, and Japanese Patent No. 6516 The following can also be used as red pigments: the red pigment described in Patent Publication No. 119, the red pigment described in Japanese Patent Publication No. 6525101, the brominated diketopyrrolopyrrole compound described in paragraph 0229 of Japanese Patent Application Publication No. 2020-090632, the anthraquinone compound described in Korean Published Patent Publication No. 10-2019-0140741, the anthraquinone compound described in Korean Published Patent Publication No. 10-2019-0140744, the perylene compound described in Japanese Patent Application Publication No. 2020-079396, and the diketopyrrolopyrrole compounds described in paragraphs 0025 to 0041 of Japanese Patent Application Publication No. 2020-066702. Furthermore, as a red pigment, compounds having a structure in which an aromatic ring group, to which an oxygen atom, sulfur atom, or nitrogen atom is bonded, is introduced, is bonded to a diketopyrrolopyrrole skeleton.

[0034] The content of other pigments in the colorant contained in the photosensitive composition is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less.

[0035] Dyes can also be used as colorants. Examples of dyes include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyromethene dyes, and the like. The dyes used in this invention are preferably blue or purple dyes because they readily form films with hues suitable for blue spectroscopy. Furthermore, the dyes are preferably xanthene dyes or triarylmethane dyes.

[0036] The colorants include diarylmethane compounds described in Japanese Patent Publication No. 2020-504758, triarylmethane dye polymers described in Korean Published Patent No. 10-2020-0028160, xanthene compounds described in Japanese Patent Publication No. 2020-117638, phthalocyanine compounds described in International Publication No. 2020 / 174991, isoindoline compounds described in Japanese Patent Publication No. 2020-160279 or salts thereof, compounds represented by Formula 1 described in Korean Published Patent No. 10-2020-0069442, and Korean Publication A compound represented by formula 1 described in Japanese Patent Publication No. 10-2020-0069730, a compound represented by formula 1 described in Korean Published Patent Publication No. 10-2020-0069070, a compound represented by formula 1 described in Korean Published Patent Publication No. 10-2020-0069067, a compound represented by formula 1 described in Korean Published Patent Publication No. 10-2020-0069062, a zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, or an isoindoline compound described in Japanese Patent Publication No. 2020-180176 can be used. The chromatic colorant may be a rotaxane, and the pigment skeleton may be used in a cyclic structure of the rotaxane, in a rod-shaped structure, or in both structures.

[0037] The total content of colorant A and pigment derivative B in the total solids of the photosensitive composition is 40% by mass or more, preferably 42% by mass or more, more preferably 45% by mass or more, and even more preferably 47% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. Furthermore, the pigment content in the total solids of the photosensitive composition is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Furthermore, the content of blue pigment in the total solid content of the photosensitive composition is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Furthermore, the content of blue pigment and purple pigment in the total solid content of the photosensitive composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and particularly preferably 30% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0038] <<Pigment derivative B>> The photosensitive composition of the present invention contains pigment derivative B (hereinafter also referred to as pigment derivative). The pigment derivative used in the photosensitive composition of the present invention includes a transparent pigment derivative B1 and a chromatic pigment derivative B2.

[0039] (Pigment derivative B1) Pigment derivative B1 has a maximum molar extinction coefficient of 3000 L·mol in the wavelength range of 400-700 nm. -1 ·cm -1 Preferably, the following: 1000 L·mol-1 ·cm -1 It is more preferable that the following conditions apply: 100 L·mol -1 ·cm -1 It is even more preferable that the following conditions are met: The lower limit of the maximum value of the above molar extinction coefficient is, for example, 1 L·mol -1 ·cm -1 That is all. 10 L·mol -1 ·cm -1 That's fine too.

[0040] It is also preferable that the pigment derivative B1 satisfies any of the following spectral characteristics (a) to (d). (a) The maximum molar extinction coefficient in the wavelength range of over 700 nm and up to 750 nm is 3000 L·mol -1 ·cm -1 Preferably, the following: 1000 L·mol -1 ·cm -1 It is more preferable that the following conditions apply: 100 L·mol -1 ·cm -1 The following is even more preferable: (b) The maximum molar extinction coefficient in the wavelength range of 750 nm to 800 nm is 3000 L·mol -1 ·cm -1 Preferably, the following: 1000 L·mol -1 ·cm -1 It is more preferable that the following conditions apply: 100 L·mol -1 ·cm -1 The following is even more preferable: (c) The maximum molar extinction coefficient in the wavelength range of over 800 nm and up to 850 nm is 3000 L·mol -1 ·cm -1 Preferably, the following: 1000 L·mol -1 ·cm -1 It is more preferable that the following conditions apply: 100 L·mol -1 ·cm -1 The following is even more preferable: (d) The maximum molar extinction coefficient in the wavelength range of over 850 nm and up to 900 nm is 3000 L·mol -1 ·cm -1Preferably, the following: 1000 L·mol -1 ·cm -1 It is more preferable that the following conditions apply: 100 L·mol -1 ·cm -1 The following is even more preferable:

[0041] Pigment derivative B1 preferably contains an aromatic ring. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. Furthermore, the aromatic ring may be a monocycle or a fused ring. Specifically, the aromatic ring is preferably an aromatic ring selected from a benzene ring, naphthalene ring, fluorene ring, perylene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, imidazoline ring, pyridine ring, triazole ring, imidazoline ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, benzimidazole ring, benzopyrazole ring, benzoxazole ring, benzothiazole ring, benzotriazole ring, indole ring, isoindole ring, triazine ring, pyrrole ring, carbazole ring, benzimidazolinone ring, phthalimide ring, phthalocyanine ring, anthraquinone ring, diketopyrrolopyrrole ring, isoindolinone ring, isoindoline ring, and quinacridone ring, or a condensed ring containing these aromatic rings. The above condensed ring may be an aromatic ring or a non-aromatic ring as a whole, but it is preferably an aromatic ring. Furthermore, while pigment derivative B1 may have only one aromatic ring or fused ring, it is preferable to have two or more aromatic rings because a greater number of aromatic rings improves pigment adsorption due to π-π interactions, making it easier to suppress pigment aggregation in the film. The above aromatic ring or fused ring may further have substituents. An example of substituent is substituent T, which will be described later.

[0042] Pigment derivative B1 is more preferably a compound having a nitrogen-containing aromatic heterocycle, and even more preferably a compound having a triazine ring. Pigment derivative B1 is particularly preferably a compound having a group represented by formula (A1). [ka] In equation (A1), * represents a bond, Ya 1 and Ya 2 Each of these independently corresponds to -N(Ra 1 )- or -O- represents, Ra 1 This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, or aryl group. B 1 and B 2 Each of these independently represents a hydrogen atom or a substituent.

[0043] Ya of equation (A1) 1 and Ya 2 Each of these independently corresponds to -N(Ra 1 -N(Ra) represents -O- or -O-, and -N(Ra) is used because it is easier to obtain the effects of the present invention more significantly. 1 ) - is preferable.

[0044] Ra 1 This represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. Ra 1 The number of carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. 1 The alkyl group represented by may have further substituents. Examples of substituents include substituent T, which will be described later. Ra 1 The number of carbon atoms in the alkenyl group represented by is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. 1 The alkenyl group represented by may have further substituents. Examples of substituents include substituent T, which will be described later. Ra 1The number of carbon atoms in the alkynyl group represented by is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkynyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. 1 The alkynyl group represented by may have further substituents. Examples of substituents include substituent T, which will be described later. Ra 1 The number of carbon atoms in the aryl group represented by Ra is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. 1 The aryl group represented by may have further substituents. Examples of substituents include substituent T, which will be described later.

[0045] B of equation (A1) 1 and B 2 Each of these independently represents a hydrogen atom or a substituent. Examples of substituents include substituent T, which will be described later, and alkyl groups, aryl groups, and heterocyclic groups are preferred, aryl groups and heterocyclic groups are more preferred, and aryl groups are even more preferred. In addition, B is preferred because it is easier to suppress color unevenness. 1 and B 2 It is also preferable that at least one of the groups is a heterocyclic group. The heterocyclic group is preferably a nitrogen-containing heterocyclic group, and more preferably a benzimidazolon group.

[0046] B 1 and B 2The alkyl, aryl, and heterocyclic groups represented by may have further substituents. Further substituents include alkyl groups (preferably C1-C30 alkyl groups), fluoroalkyl groups (preferably C1-C30 fluoroalkyl groups), alkenyl groups (preferably C2-C30 alkenyl groups), alkynyl groups (preferably C2-C30 alkynyl groups), aryl groups (preferably C6-C30 aryl groups), amino groups (preferably C0-C30 amino groups), alkoxy groups (preferably C1-C30 alkoxy groups), aryloxy groups (preferably C6-C30 aryloxy groups), heterocyclic groups. Roaryloxy group, acyl group (preferably acyl group having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), acyloxy group (preferably acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably acylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably (C7-C30 aryloxycarbonylamino group), sulfamoyl group (preferably C0-C30 sulfamoyl group), carbamoyl group (preferably C1-C30 carbamoyl group), alkylthio group (preferably C1-C30 alkylthio group), arylthio group (preferably C6-C30 arylthio group), heteroarylthio group (preferably C1-C30 heteroarylthio group), alkylsulfonyl group (preferably C1-C30 alkylsulfonyl group), arylsulfonyl group (preferably carbon (aryl sulfonyl groups having 6 to 30 carbon atoms), heteroaryl sulfonyl groups (preferably heteroaryl sulfonyl groups having 1 to 30 carbon atoms), alkyl sulfinyl groups (preferably alkyl sulfinyl groups having 1 to 30 carbon atoms), aryl sulfinyl groups (preferably aryl sulfinyl groups having 6 to 30 carbon atoms), heteroaryl sulfinyl groups (preferably heteroaryl sulfinyl groups having 1 to 30 carbon atoms), ureido groups (preferably ureido groups having 1 to 30 carbon atoms), phosphate amide groups (preferably phosphate amide groups having 1 to 30 carbon atoms), hydroxyl groups,Examples of groups include carboxyl groups, sulfo groups, phosphate groups, mercapto groups, halogen atoms, cyano groups, alkylsulfino groups, arylsulfino groups, hydrazino groups, and imino groups. Alkyl groups, fluoroalkyl groups, alkoxy groups, amino groups, halogen atoms, alkenyl groups, hydroxyl groups, alkoxycarbonyl groups, acyloxy groups, acylamino groups, and nitro groups are preferred. The above further substituents may be acidic or basic groups. The acidic group is preferably at least one selected from carboxyl groups, sulfo groups, phosphate groups and their salts, and more preferably at least one selected from carboxyl groups, sulfo groups and their salts. The atoms or groups of atoms constituting the salt may be alkali metal ions (Li + na + , K + (e.g.), alkaline earth metal ions (Ca 2+ Mg 2+ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. The basic group is preferably at least one selected from amino groups, pyridyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups, more preferably at least one selected from amino groups, salts of amino groups, and salts of ammonium groups, and more preferably an amino group or a salt of an amino group. Examples of amino groups include -NH2, dialkylamino groups, alkylarylamino groups, diarylamino groups, and cyclic amino groups. Dialkylamino groups, alkylarylamino groups, diarylamino groups, and cyclic amino groups may further have substituents. Examples of substituents include the substituent T mentioned above. Examples of atoms or groups of atoms constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions. B 1 and B 2 The alkyl group, aryl group, and heterocyclic group represented may also preferably not have the further substituents mentioned above.

[0047] (substituent T) Examples of the substituent T include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -ORt 1 、-CORt 1 、-COORt 1 、-OCORt 1 、-NRt 1 Rt 2 、-NHCORt 1 、-CONRt 1 Rt 2 、-NHCONRt 1 Rt 2 、-NHCOORt 1 、-SRt 1 、-SO2Rt 1 、-SO2ORt 1 、-NHSO2Rt 1 or -SO2NRt 1 Rt 2 Examples of Rt 1 and Rt 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. Rt 1 and Rt 2 may combine to form a ring.

[0048] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, with linear or branched being preferred and linear being more preferred. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic, with linear or branched being preferred and linear being more preferred. The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, with linear or branched being preferred and linear being more preferred. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The heterocyclic group may be a monocyclic ring or a fused ring. A monocyclic ring or a fused ring with 2 to 4 fusions is preferred. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclic group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and heterocyclic groups may have substituents or may be unsubstituted. Examples of substituents include those listed above as substituent T.

[0049] Specific examples of aromatic rings in pigment derivative B1 include the group with the following structure and Z, which will be discussed later. 1 Examples of this include the structural groups shown. In the following structural formulas, Me represents a methyl group.

[0050] [ka] [ka] [ka] [ka]

[0051] Pigment derivative B1 preferably contains at least one group selected from acidic groups and basic groups. The acidic group is preferably at least one selected from carboxyl groups, sulfo groups, phosphate groups and their salts, and more preferably at least one selected from carboxyl groups, sulfo groups and their salts. The atoms or groups of atoms constituting the salt may be alkali metal ions (Li + na + , K + (e.g.), alkaline earth metal ions (Ca 2+ Mg 2+Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. The basic group is preferably at least one selected from amino groups, pyridyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups, more preferably at least one selected from amino groups, salts of amino groups, and salts of ammonium groups, and more preferably an amino group or a salt of an amino group. Examples of amino groups include -NH2, dialkylamino groups, alkylarylamino groups, diarylamino groups, and cyclic amino groups. Dialkylamino groups, alkylarylamino groups, diarylamino groups, and cyclic amino groups may further have substituents. Examples of substituents include the substituent T mentioned above. Examples of atoms or groups of atoms constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0052] The pigment derivative B1 is preferably a compound represented by the following formula (b1). A 1 -L 1 -Z 1 ...(b1) In formula (b1), A 1 This represents a group containing an aromatic ring, L 1 This represents a single bond or a divalent linking group. Z 1 This represents a group that has an acidic or basic group.

[0053] A in equation (b1) 1 A represents a group containing an aromatic ring. 1 The aromatic ring contained in may be an aromatic hydrocarbon ring or an aromatic heterocycle. Furthermore, the aromatic ring may be a monocycle or a fused ring. A 1The group represented by includes groups containing aromatic rings selected from benzene rings, naphthalene rings, fluorene rings, perylene rings, imidazole rings, pyrazole rings, oxazole rings, thiazole rings, imidazoline rings, pyridine rings, triazole rings, imidazoline rings, pyrazine rings, pyrimidine rings, pyridazine rings, quinoline rings, isoquinoline rings, quinoxaline rings, quinazoline rings, benzimidazole rings, benzopyrazole rings, benzoxazole rings, benzothiazole rings, benzotriazole rings, indole rings, isoindole rings, triazine rings, pyrrole rings, carbazole rings, benzimidazolinone rings, phthalimide rings, phthalocyanine rings, anthraquinone rings, diketopyrrolopyrrole rings, isoindolinone rings, isoindoline rings, and quinacridone rings; and groups containing fused rings that include these aromatic rings. The above fused rings may be aromatic rings or non-aromatic rings, but aromatic rings are preferred.

[0054] A 1 The group represented by may have further substituents. Examples of substituents include the substituent T mentioned above.

[0055] A 1 The group represented by is preferably a group containing a benzimidazolinone ring or a group represented by the above formula (A1), and more preferably a group represented by the above formula (A1). 1 If the base is represented by formula (Z1) described later, then A 1 It is particularly preferable that the group is represented by the base formula (A1).

[0056] L in equation (b1) 1 L represents a single bond or a divalent linking group, and a divalent linking group is preferred. 1 The divalent linking groups represented by include alkylene groups, arylene groups, heterocyclic groups, -O-, and -N(R). L1Examples include -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2-, and combinations thereof. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 8, and particularly preferably 1 to 5. The alkylene group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being particularly preferred. The number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 15. The arylene group is preferably a phenylene group. L1 R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. L1 The preferred range of alkyl groups, alkenyl groups, alkynyl groups, and aryl groups represented by Ra 1 The preferred ranges for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups are the same as those described above.

[0057] L 1 The divalent linking group represented by is preferably the group represented by the following formula (L1). -L 1A -L 1B -L 1C - ···(L1) In the formula, L 1A and L 1C These are independent of each other: -O-, -N(R L1 )-, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, or -SO2-, L 1B This represents a single bond or a divalent linking group.

[0058] L 1B The divalent linking groups represented by include alkylene groups, arylene groups, and single bonds between alkylene and arylene groups, or -O-, -N(R L1 Groups bonded via groups consisting of -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2- and combinations thereof, alkylene groups bonded to each other or arylene groups bonded to each other -O-, -N(R L1Examples include groups bonded via groups consisting of -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2-, and combinations thereof.

[0059] L 1 A concrete example of this is the base structure shown below. [ka]

[0060] Z in equation (b1) 1 This represents a group having an acidic or basic group. The types of acidic and basic groups include those listed above.

[0061] Z in equation (b1) 1 It is preferable that the group is represented by formula (Z1) or formula (Z10).

[0062] [ka] In equation (Z1), * represents a bond, Yz 1 is -N(Ry 1 )- or -O- represents, Ry 1 This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, or aryl group. Lz 1 This represents a divalent linking group, Rz 1 and Rz 2 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. Rz 1 and Rz 2 They may also be bonded via a divalent group to form a ring. m represents an integer between 1 and 5. [ka]

[0063] In equation (Z10), * represents a bond, and Lc 1 and Lc 2 Each of these independently represents a single bond or a linking group, and Rc 1 and Rc 2 Each of these independently represents a substituent, and Rc 1 and Rc 2 At least one of them represents an acidic group or a basic group.

[0064] First, let's explain equation (Z1). In equation (Z1), Yz 1 is -N(Ry 1 )- or -O- represents -N(Ry 1 ) - Preferably Ry 1 Ry represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. 1 The preferred range of alkyl groups, alkenyl groups, alkynyl groups, and aryl groups represented by Ra 1 The preferred ranges for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups are the same as those described above.

[0065] In equation (Z1), Lz 1 The divalent linking groups represented by include alkylene groups, arylene groups, heterocyclic groups, -O-, and -N(R). L1 Examples include -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2-, and combinations thereof, with alkylene groups being preferred. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 8, and particularly preferably 1 to 5. The alkylene group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being particularly preferred.

[0066] In equation (Z1), Rz 1 and Rz 2Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and is preferably an alkyl group or an aryl group, more preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1 or 2. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 10, more preferably 2 to 8, and particularly preferred to 2 to 5. The alkenyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. The number of carbon atoms in the alkynyl group is preferably 2 to 10, more preferably 2 to 8, and particularly preferred to 2 to 5. The alkynyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.

[0067] In equation (Z1), Rz 1 and Rz 2 These may be bonded via a divalent group to form a ring. Examples of divalent groups include -CH2-, -O-, and -SO2-. Rz 1 and Rz 2 The following are specific examples of rings formed via a divalent group. [ka]

[0068] In formula (Z1), m represents an integer from 1 to 5, preferably from 1 to 4, more preferably from 1 to 3, even more preferably 2 or 3, and particularly preferably 2.

[0069] The group represented by formula (Z1) is preferably the group represented by the following formula (Z2). [ka] In equation (Z2), * represents a bond, Yz 2 and Yz 3Each of these independently corresponds to -N(Ry 2 )- or -O- represents, Ry 2 This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, or aryl group. Lz 2 and Lz 3 Each of these independently represents a divalent linking group, Rz 3 ~Rz 6 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. Rz 3 and Rz 4 , and Rz 5 and Rz 6 These may be bonded together via divalent groups to form a ring.

[0070] Yz in equation (Z2) 2 and Yz 3 This is Yz in equation (Z1). 1 This is synonymous with the same thing, and the preferred range is also the same. 2 Ry represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. 2 The preferred range of alkyl groups, alkenyl groups, alkynyl groups, and aryl groups represented by Ra 1 The preferred ranges for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups are the same as those described above.

[0071] Lz in equation (Z2) 2 and Lz 3 Lz in equation (Z1) 1 This is synonymous with the same as the preferred range. Rz in equation (Z2) 3 ~Rz 6 Rz in equation (Z1) 1 and Rz 2 This is synonymous with the same thing, and the preferred range is also similar.

[0072] Next, we will explain equation (Z10). In equation (Z10), Lc 1 and Lc 2 Each of these independently represents a single bond or a linking group, and it is preferable that they be divalent linking groups. Examples of divalent linking groups include alkylene groups, arylene groups, -O-, and -N(R L1 Examples include -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2-, and combinations thereof. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 8, and particularly preferably 1 to 5. The alkylene group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being particularly preferred. The number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 15. The arylene group is preferably a phenylene group. L1 R represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. L1 The number of carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. L1 The alkyl group represented by may have further substituents. Examples of substituents include the substituent T mentioned above. L1 The number of carbon atoms in the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. L1 The aryl group represented by may have further substituents. Examples of substituents include the substituent T mentioned above.

[0073] In equation (Z10), Rc 1 and Rc 2 Each of these independently represents a substituent. Examples of substituents include alkyl groups, aryl groups, heterocyclic groups, hydroxyl groups, acidic groups, and basic groups. However, Rc 1 and Rc 2 At least one of them represents an acidic group or a basic group. Rc 1 and Rc 2 At least one of them is preferably a basic group, Rc1 and Rc 2 It is more preferable that both are basic groups. Examples of acidic and basic groups include those mentioned above. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The heterocyclic group may be monocyclic or fused. The heterocyclic group is preferably monocyclic or a fused ring with 2 to 4 fusions. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclic group are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The alkyl group, aryl group, and heterocyclic group may further have substituents. Examples of substituents include the substituent T mentioned above.

[0074] The group represented by the above formula (Z10) is preferably the group represented by the following formula (Z11), and more preferably the group represented by the following formula (Z12). [ka]

[0075] In equation (Z11), * represents a coupling, Lc 11 and Lc 12 Each of these independently represents a single bond or a linking group, and Rc 11 and Rc 12 Each of these independently represents a hydrogen atom or a substituent, and Rc 13 and Rc 14 Each of these independently represents a substituent, and Rc 13 and Rc 14 At least one of them represents an acidic group or a basic group.

[0076] Rc in equation (Z11) 13 and Rc 14 Rc in equation (Z10) 1 and Rc2 This is synonymous with the same thing, and the preferred range is also similar.

[0077] In equation (Z11), Rc 11 and Rc 12 Each of these independently represents a hydrogen atom or a substituent. Rc 11 and Rc 12 Examples of substituents represented by include alkyl groups and aryl groups. The alkyl group has 1 to 20 carbon atoms, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. The aryl group has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The alkyl and aryl groups may have further substituents. Examples of substituents include the substituent T mentioned above. Rc 11 and Rc 12 It is preferable that it is a hydrogen atom.

[0078] In equation (Z11), Lc 11 and Lc 12 Each of these independently represents a single bond or a linking group, and it is preferable that they be divalent linking groups. Examples of divalent linking groups include alkylene groups, arylene groups, -O-, and -N(R L11 Examples include -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2- and combinations thereof, and it is preferable that the group contains at least one selected from alkylene groups and arylene groups, more preferably a group containing an alkylene group, and even more preferably an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 8, and particularly preferably 1 to 5. The alkylene group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being particularly preferred. The number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 15. The arylene group is preferably a phenylene group. L1 R represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.L11 The alkyl and aryl groups represented by are as described above. L1 This is synonymous with alkyl and aryl groups represented by .

[0079] [ka]

[0080] In equation (Z12), * represents a coupling, and Lc 21 and Lc 22 Each of these independently represents a single bond or a linking group, and Rc 21 and Rc 22 Each of these independently represents a hydrogen atom or a substituent, and Rc 23 ~Rc 26 Each of these independently represents a hydrogen atom or a substituent, and Rc 23 and Rc 24 The Rc group may be bonded via a divalent group to form a ring. 25 and Rc 26 These may be bonded via a divalent group to form a ring.

[0081] Rc in equation (Z12) 21 and Rc 22 Rc in equation (Z11) 11 and Rc 12 This is synonymous with the same as the preferred range. Lc in equation (Z12) 21 and Lc 22 Lc in equation (Z11) 11 and Lc 12 This is synonymous with the same thing, and the preferred range is also similar.

[0082] In equation (Z12), Rc 23 ~Rc 26Each of these independently represents a hydrogen atom or a substituent, and is preferably a substituent. Examples of substituents include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The alkyl group and aryl group may have further substituents. Examples of substituents include the substituent T mentioned above.

[0083] In equation (Z12), Rc 23 and Rc 24 The Rc group may be bonded via a divalent group to form a ring. 25 and Rc 26 These groups may be bonded together via divalent groups to form a ring. Examples of divalent groups include -CH2-, -O-, and -SO2-. Specific examples of rings formed by these groups via divalent groups are as follows: [ka]

[0084] Z 1 A specific example is the group with the following structure. In the following structural formula, Ph represents a phenyl group. [ka] [ka]

[0085] The pigment derivative B1 is preferably a compound represented by the following formula (b2). By using such a compound, the effects of the present invention can be obtained more significantly. A 1 -X 1 -L 2 -X 2 -Z 1 ...(b2) In formula (b2), A 1 This represents a group containing an aromatic ring, X 1 and X 2 These are, independently, single bonds, -O-, and -N(R) 1 )-, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, or -SO2- R 1 This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, or aryl group. L 2 This represents a single bond or a divalent linking group. Z 1 This represents the group expressed by the formula (Z1) described above.

[0086] A in equation (b2) 1 and Z 1 is A in equation (b1) 1 and Z 1 This is synonymous with the same thing, and the preferred range is also similar.

[0087] X in equation (b2) 1 and X 2 These are, independently, single bonds, -O-, and -N(R) 1 )-, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, or -SO2-, and -O-, -N(R 1 It is preferable that the molecule is -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, or -SO2-. 1 R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. 1 The preferred range of alkyl groups, alkenyl groups, alkynyl groups, and aryl groups represented by Ra 1 The preferred ranges for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups are the same as those described above.

[0088] L in equation (b2) 2L represents a single bond or a divalent linking group. 2 The divalent linking groups represented by include alkylene groups, arylene groups, and single bonds between alkylene and arylene groups, or -O-, -N(R 2 Groups bonded via groups consisting of -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2- and combinations thereof, alkylene groups bonded to each other or arylene groups bonded to each other -O-, -N(R 2 Examples include groups bonded via groups consisting of -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO2NH-, -SO2-, and combinations thereof. 2 R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. 2 The preferred range of alkyl groups, alkenyl groups, alkynyl groups, and aryl groups represented by Ra 1 The preferred ranges for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups are the same as those described above.

[0089] Specific examples of pigment derivative B1 include the compounds shown below and the compounds described in the examples below. In the table below, A 1 Structure, L 1 Structure, Z 1 The symbols listed in the structure column are A 1 Specific examples (that is, specific examples of the base represented by the above formula (A1)), L 1 A concrete example of Z 1 This is the structure mentioned in the specific example. [Table 1]

[0090] (Pigment derivative B2) Next, pigment derivative B2 will be described. Pigment derivative B2 is a chromatic pigment derivative. Examples of pigment derivative B2 include compounds having a structure in which a portion of the chromophore is substituted with an acidic or basic group.

[0091] The acidic group is preferably at least one selected from a carboxyl group, a sulfo group, a phosphate group, and their salts, and more preferably at least one selected from a carboxyl group, a sulfo group, and their salts. The atoms or groups of atoms constituting the salt are alkali metal ions (Li + na + , K + (e.g.), alkaline earth metal ions (Ca 2+ Mg 2+ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. The basic group is preferably at least one selected from amino groups, pyridyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups, more preferably at least one selected from amino groups, salts of amino groups, and salts of ammonium groups, and more preferably an amino group or a salt of an amino group. Examples of amino groups include -NH2, dialkylamino groups, alkylarylamino groups, diarylamino groups, and cyclic amino groups. Dialkylamino groups, alkylarylamino groups, diarylamino groups, and cyclic amino groups may further have substituents. Examples of substituents include the substituent T mentioned above. Examples of atoms or groups of atoms constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0092] Examples of chromophores constituting pigment derivative B2 include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, surene skeleton, and metal complex skeleton. Phthalocyanine skeleton, benzimidazolone skeleton, and dioxazine skeleton are preferred, and phthalocyanine skeleton is more preferred, because they tend to form films with superior lightfastness. In other words, pigment derivative B2 is preferably a phthalocyanine compound, a benzimidazolone compound, or a dioxazine compound, and more preferably a phthalocyanine compound.

[0093] The maximum absorption wavelength of pigment derivative B2 is preferably in the wavelength range of 400 to 700 nm. The hues exhibited by pigment derivative B2 include blue, purple, red, yellow, and green, but blue or purple is preferred because it is easier to form a film with better lightfastness.

[0094] The maximum molar extinction coefficient of pigment derivative B2 in the 400-700 nm wavelength range is 10,000 L·mol. -1 ·cm -1 Preferably, it should be 15,000 L·mol or more. -1 ·cm -1 It is more preferable that the above is true, and 20,000 L·mol -1 ·cm -1 It is even more preferable that the above is true. The upper limit is 200,000 L·mol. -1 ·cm -1 The following is preferable:

[0095] The difference between the maximum molar extinction coefficient of pigment derivative B2 in the 400-700 nm wavelength range and the maximum molar extinction coefficient of pigment derivative B1 in the 400-700 nm wavelength range is 10,000 L·mol. -1 ·cm -1 Preferably, the amount is 20,000 L·mol or more. -1 ·cm -1It is more preferable that the above is true, and 30,000 L·mol -1 ·cm -1 It is even more preferable that the above is true. The upper limit is 200,000 L·mol. -1 ·cm -1 The following is preferable:

[0096] If pigment derivative B1 is a compound having an acidic group, then it is preferable that pigment derivative B2 is a compound having an acidic group. Furthermore, if pigment derivative B1 is a compound having a basic group, it is preferable that pigment derivative B2 is a compound having a basic group.

[0097] The content of pigment derivative B in the total solid content of the photosensitive composition is preferably 0.5 to 40% by mass. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less.

[0098] Furthermore, the content of pigment derivative B is preferably 1 to 60 parts by mass per 100 parts by mass of the total of colorant A and pigment derivative B. The lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

[0099] Furthermore, the content of pigment derivative B2 is preferably 1 to 90 parts by mass per 100 parts by mass of the total pigment derivative B1. The lower limit is preferably 2 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less.

[0100] <<Resin C>> The photosensitive composition of the present invention contains resin C (hereinafter referred to as resin). The resin is formulated, for example, for the use of dispersing pigments in the photosensitive composition or for the use as a binder. The resin mainly used for dispersing pigments in the photosensitive composition is also referred to as a dispersant. The resin as a dispersant can be used when preparing a dispersion liquid. However, such uses of the resin are only examples, and the resin can also be used for purposes other than such uses.

[0101] The weight average molecular weight (Mw) of the resin is preferably from 2000 to 2000000. The upper limit is preferably 1000000 or less, more preferably 500000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more.

[0102] Examples of resins include (meth)acrylic resin, (meth)acrylamide resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin. Furthermore, the resin described in paragraphs 0041 to 0060 of JP 2017-206689, the resin described in paragraphs 0022 to 0071 of JP 2018-010856, the resin described in JP 2017-057265, the resin described in JP 2017-032685, the resin described in JP 2017-075248, the resin described in JP 2017-066240, the resin described in JP 2020-122052, the resin described in JP 2020-111656, and JP 2020-139 The following resins can be used: the resin described in Japanese Patent Publication No. 021, the alkali-soluble resin having a urea functional group described in Japanese Patent Application Publication No. 2020-139021, the resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in Japanese Patent Application Publication No. 2017-138503, the resin described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Application Publication No. 2020-186325, and the resin represented by formula 1 described in Korean Published Patent No. 10-2020-0078339. In addition, a resin with a glass transition temperature of 390°C or higher can be used as the resin. A commercially available resin with a glass transition temperature of 390°C or higher is polyimide varnish H520 manufactured by Mitsubishi Gas Chemical Company, Inc.

[0103] As the resin, it is preferable to use a resin having an acid group. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group, and the like. These acid groups may be only one kind or two or more kinds. The resin having an acid group can be used, for example, as an alkali-soluble resin. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

[0104] As the resin, it is also preferable to include a resin containing a repeating unit derived from a compound represented by formula (ED1) and / or a compound represented by formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimer").

[0105]

Chemical formula

[0106] In formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

Chemical formula

[0107] Regarding specific examples of the ether dimer, paragraph number 0317 of JP-A-2013-029760 can be referred to, and this content is incorporated herein.

[0108] A resin having basic groups can also be used as the resin. Examples of resins having basic groups include copolymers having repeating units with basic groups in their side chains and repeating units without basic groups. Resins having basic groups can also be used as dispersants. The amine value of the resin having basic groups is preferably 5 to 300 mg KOH / g. The lower limit is preferably 10 mg KOH / g or more, and more preferably 20 mg KOH / g or more. The upper limit is preferably 200 mg KOH / g or less, and more preferably 100 mg KOH / g or less. Commercially available resins containing basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by Bic Chemie Co., Ltd.), and Solspers 112. Examples include 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc. Furthermore, the resin having basic groups may also be the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Publication No. 2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Publication No. 2018-156021, or the vinyl resin having basic groups described in paragraphs 0150 to 0153 of Japanese Patent Publication No. 2019-184763, and these details are incorporated herein by reference.

[0109] It is also preferable to use a resin having ethylenically unsaturated bond-containing groups as the resin. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. The ethylenically unsaturated bond-containing value of the resin (hereinafter also referred to as the C=C value) is preferably 0.01 to 2.0 mmol / g, more preferably 0.1 to 1.5 mmol / g, and even more preferably 0.1 to 1.0 mmol / g from the viewpoint of developability and curability. The C=C value of the resin is a numerical value that represents the molar amount of ethylenically unsaturated bond-containing groups per gram of solid content of the resin. For resins where the C=C value can be calculated from the raw materials used in the synthesis of the resin, the value calculated from the raw materials used in the preparation is used. For resins where the C=C value cannot be calculated from the raw materials used in the synthesis of the resin, the value measured by hydrolysis is used. Specifically, the low-molecular-weight component (a) containing ethylenically unsaturated bond groups is extracted from the resin by alkaline treatment, its content is measured by high-performance liquid chromatography (HPLC), and the value is calculated using the following formula. Furthermore, if the low-molecular-weight component (a) cannot be extracted from the resin by alkaline treatment, the value measured by NMR (nuclear magnetic resonance) is used. The carbon content of the resin = carbon value [mmol / g] = (content of low molecular weight component (a) [ppm] / molecular weight of low molecular weight component (a) [g / mol]) / (weight of the resin [g] × (solid content concentration of the resin [mass%] / 100) × 10)

[0110] As the resin, it is also preferable to use a resin that contains repeating units derived from the compound represented by formula (X). [ka] In the formula, R 1 R represents a hydrogen atom or a methyl group. 21 and R 22 Each of these independently represents an alkylene group, and n is an integer from 0 to 15. 21 and R 22The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 or 3. n represents an integer from 0 to 15, preferably an integer from 0 to 5, more preferably an integer from 0 to 4, and even more preferably an integer from 0 to 3.

[0111] Compounds represented by formula (X) include ethylene oxide or propylene oxide-modified (meth)acrylates of paracumylphenol. Commercially available products include Aronics M-110 (manufactured by Toagosei Co., Ltd.).

[0112] As the resin, it is also preferable to use a resin having aromatic carboxyl groups (hereinafter also referred to as resin Ac). In resin Ac, aromatic carboxyl groups may be included in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferable that aromatic carboxyl groups are included in the main chain of the repeating unit. In this specification, an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In an aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.

[0113] The resin Ac is preferably a resin containing at least one repeating unit selected from the repeating units represented by formula (Ac-1) and the repeating units represented by formula (Ac-2). [ka] In formula (Ac-1), Ar 1 L represents a group containing an aromatic carboxyl group. 1 represents -COO- or -CONH-, L 2 This represents a divalent linking group. In formula (Ac-2), Ar 10 L represents a group containing an aromatic carboxyl group. 11 represents -COO- or -CONH-, L 12 represents a trivalent linking group, P10 represents a polymer chain.

[0114] In formula (Ac-1), Ar 1 Examples of the group containing an aromatic carboxy group represented by include a structure derived from an aromatic tricarboxylic anhydride, a structure derived from an aromatic tetracarboxylic anhydride, and the like. Examples of the aromatic tricarboxylic anhydride and the aromatic tetracarboxylic anhydride include compounds having the following structures. [Chemical formula]

[0115] In the above formula, Q 1 represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2). [Chemical formula]

[0116] Ar 1 The group containing an aromatic carboxy group represented by may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group. Ar 1 Specific examples of the group containing an aromatic carboxy group represented by include a group represented by formula (Ar-11), a group represented by formula (Ar-12), a group represented by formula (Ar-13), and the like. [Chemical formula]

[0117] In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2. In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 2. In formula (Ar-13), n3 and n4 each independently represent integers between 0 and 4, preferably between 0 and 2, more preferably 1 or 2, and even more preferably 1. However, at least one of n3 and n4 is an integer of 1 or greater. In formula (Ar-13), Q 1 This represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by formula (Q-1) above, or a group represented by formula (Q-2) above. In equations (Ar-11) to (Ar-13), *1 is L 1 This indicates the connection point with [the other element].

[0118] In equation (Ac-1), L 1 This represents -COO- or -CONH-, and is preferably -COO-.

[0119] In equation (Ac-1), L 2 Examples of divalent linking groups represented by include alkylene groups, arylene groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations of two or more of these. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The alkylene and arylene groups may have substituents. Examples of substituents include hydroxyl groups. 2 The divalent linking group represented by is -L 2a It is preferable that the group is represented by -O-. 2aExamples of alkylene groups include alkylene groups, arylene groups, groups combining alkylene and arylene groups, and groups combining at least one selected from alkylene and arylene groups with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, with alkylene groups being preferred. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The alkylene group may be linear, branched, or cyclic. The alkylene and arylene groups may have substituents. Examples of substituents include hydroxyl groups.

[0120] In equation (Ac-2), Ar 10 The group containing the aromatic carboxyl group represented by is the Ar of formula (Ac-1). 1 This is synonymous with the same thing, and the preferred range is also similar.

[0121] In equation (Ac-2), L 11 This represents -COO- or -CONH-, and is preferably -COO-.

[0122] In equation (Ac-2), L 12 The trivalent linking group represented by includes hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups combining two or more of these. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have substituents. Examples of substituents include hydroxyl groups. 12 The trivalent linking group represented by is preferably the group represented by formula (L12-1), and more preferably the group represented by formula (L12-2). [ka]

[0123] In formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, and *1 is L in equation (Ac-2). 11 This represents the bond position with, and *2 is P in equation (Ac-2). 10 This indicates the connection position with L. 12b Examples of trivalent linking groups represented by include hydrocarbon groups; groups formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and it is preferable that the group is a hydrocarbon group or a group formed by combining a hydrocarbon group with -O-.

[0124] In formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, and *1 is L in equation (Ac-2). 11 This represents the bond position with, and *2 is P in equation (Ac-2). 10 This indicates the connection position with L. 12c Examples of trivalent linking groups represented by include hydrocarbon groups; and groups formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, with hydrocarbon groups being preferred.

[0125] In equation (Ac-2), P 10 P represents a polymer chain. 10 The polymer chain represented by preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units, and polyol repeating units. Polymer chain P 10 The weight-average molecular weight is preferably 500 to 20000. The lower limit is preferably 1000 or more. The upper limit is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less. 10 If the weight-average molecular weight is within the above range, the dispersibility of the pigment in the composition is good. If the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.

[0126] P 10 The polymer chain represented by may contain polymerizable groups. Examples of polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.

[0127] It is also preferable to use a resin having the structure represented by formula (P-3-1) as the resin. This resin is preferably used as a dispersant. [ka] In formula (P-3-1), Rp 1 represents an alkylene group, Rp 2 'n' represents a hydrogen atom or substituent, n represents a number between 10 and 1000, and y represents a number between 1 and 2.

[0128] Rp 1 The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 or 3. 1 It is preferable that it is an ethylene group. Rp 2 Examples of substituents represented by include alkyl groups, aryl groups, and heteroaryl groups, with alkyl groups being preferred. The alkyl group preferably has 5 to 30 carbon atoms. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and branched being more preferred.

[0129] The weight-average molecular weight of the resin having the structure represented by formula (P-3-1) is preferably 2,000 to 50,000, more preferably 3,000 to 45,000, and even more preferably 4,000 to 40,000.

[0130] The acid value of the resin having the structure represented by formula (P-3-1) is preferably 10 to 200 mg KOH / g, more preferably 20 to 150 mg KOH / g, and even more preferably 30 to 120 mg KOH / g.

[0131] The photosensitive composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acidic groups is greater than the amount of basic groups. As an acidic dispersant (acidic resin), it is preferable that the amount of acidic groups is 70 mol% or more when the total amount of acidic groups and basic groups is 100 mol%. Examples of acidic groups in an acidic dispersant (acidic resin) include carboxyl groups, sulfol groups, and phosphate groups, with carboxyl groups being preferred. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH / g. Furthermore, a basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acidic groups. As a basic dispersant (basic resin), it is preferable that the amount of basic groups exceeds 50 mol% when the total amount of acidic groups and basic groups is 100 mol%. The basic group in a basic dispersant is preferably an amino group.

[0132] The resin used as a dispersant is preferably a graft resin. Details of graft resins can be found in paragraphs 0025 to 0094 of Japanese Patent Application Publication No. 2012-255128, which are incorporated herein by reference.

[0133] The resin used as a dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of its main chain and side chains. Preferably, the polyimine-based dispersant has a main chain having a substructure with functional groups having a pKa of 14 or less, and side chains with 40 to 10,000 atoms, and contains a basic nitrogen atom in at least one of its main chain and side chains. The basic nitrogen atom is not particularly limited as long as it exhibits basic properties. For polyimine-based dispersants, refer to paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, the contents of which are incorporated herein by reference.

[0134] The resin used as a dispersant is preferably a resin with a structure in which multiple polymer chains are bonded to the core. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0135] The resin used as a dispersant is preferably a resin having ethylenically unsaturated bond-containing groups. The C=C value (ethylenically unsaturated bond-containing group value) of the resin having ethylenically unsaturated bond-containing groups is preferably 0.01 to 2.0 mmol / g, more preferably 0.1 to 1.5 mmol / g, and even more preferably 0.1 to 1.0 mmol / g. From the viewpoint of developability and pigment dispersibility, the above-mentioned resin having ethylenically unsaturated bond-containing groups is also preferably further having acidic groups.

[0136] As a dispersant, the resin described in Japanese Patent Publication No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, polyethyleneimine having polyester side chains described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066687, the block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066688, and the dispersant described in International Publication No. 2016 / 104803 can also be used.

[0137] Dispersants are also available commercially. Specific examples include the Disperbyk series from Bic Chemie (e.g., Disperbyk-111, 161, 2001, etc.), the Solspers series from Lubrizol Nippon Co., Ltd. (e.g., Solspers 20000, 76500, etc.), and the Ajisper series from Ajinomoto Fine Techno Co., Ltd. Additionally, the products described in paragraph 0129 of Japanese Patent Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Publication No. 2017-194662 can also be used as dispersants.

[0138] The resin content in the total solids of the photosensitive composition is preferably 5 to 50% by mass. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more.

[0139] Furthermore, the dispersant content is preferably 1 to 100 parts by mass per 100 parts by mass of colorant. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.

[0140] Furthermore, the dispersant content is preferably 50 to 1500 parts by mass per 100 parts by mass of the pigment derivative. The lower limit is preferably 100 parts by mass or more. The upper limit is preferably 1000 parts by mass or less, and more preferably 500 parts by mass or less. The photosensitive composition of the present invention may contain only one type of resin, or it may contain two or more types of resins. When two or more types of resins are included, it is preferable that their total amount is within the above range.

[0141] <<Polymerizable monomers>> The photosensitive composition of the present invention preferably contains a polymerizable monomer. The polymerizable monomer is preferably a compound having an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. The polymerizable monomer used in the present invention is preferably a radical polymerizable monomer.

[0142] The molecular weight of the polymerizable monomer is preferably between 100 and 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0143] The polymerizable monomer is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three to fifteen ethylenically unsaturated bond-containing groups, and even more preferably a compound containing three to six ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable monomer is preferably a (meth)acrylate compound with 3 to 15 functions, and more preferably a (meth)acrylate compound with 3 to 6 functions. Specific examples of polymerizable monomers include the compounds described in paragraphs 0095 to 0108 of Japanese Patent Publication No. 2009-288705, paragraph 0227 of Japanese Patent Publication No. 2013-029760, paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970, paragraphs 0034 to 0038 of Japanese Patent Publication No. 2013-253224, paragraph 0477 of Japanese Patent Publication No. 2012-208494, Japanese Patent Publication No. 2017-048367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807, the contents of which are incorporated herein by reference.

[0144] Preferred polymerizable monomers include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and compounds in which the (meth)acryloyl groups of these compounds are linked via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer). Furthermore, polymerizable monomers include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-TMMT), and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD). Other options include HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronics TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (both manufactured by Taisei Fine Chemical Co., Ltd.), and Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0145] Furthermore, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate can also be used as polymerizable monomers. Commercially available trifunctional (meth)acrylate compounds include Aronics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0146] Furthermore, polymerizable monomers can also be compounds having an acidic group. Examples of acidic groups include carboxyl groups, sulfol groups, and phosphate groups, with carboxyl groups being preferred. Commercially available polymerizable monomers having an acidic group include Arronix M-510, M-520, and Arronix TO-2349 (manufactured by Toagosei Co., Ltd.). The preferred acid value of polymerizable monomers having an acidic group is 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g.

[0147] Polymerizable monomers can also be compounds containing a caprolactone structure. Commercially available polymerizable monomers containing a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.).

[0148] Polymerizable monomers can also be polymerizable monomers having alkylene oxy groups. Of the polymerizable monomers having alkylene oxy groups, polymerizable monomers having ethylene oxy groups and / or propylene oxy groups are preferred, polymerizable monomers having ethylene oxy groups are more preferred, and 3-6 functional (meth)acrylate compounds having 4-20 ethylene oxy groups are even more preferred. Examples of commercially available polymerizable monomers having alkylene oxy groups include SR-494, a tetrafunctional (meth)acrylate having 4 ethylene oxy groups manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutylene oxy groups manufactured by Nippon Kayaku Co., Ltd.

[0149] Polymerizable monomers can also be those having a fluorene skeleton. Examples of commercially available polymerizable monomers having a fluorene skeleton include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0150] As polymerizable monomers, it is also preferable to use compounds that are substantially free of environmentally regulated substances such as toluene. Examples of commercially available such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

[0151] The polymerizable monomer content in the total solids of the photosensitive composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 15% by mass or less. Only one polymerizable monomer may be used, or two or more may be used. When two or more are used, it is preferable that their total amount is within the above range.

[0152] <Photopolymerization initiator> The photosensitive composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitive to light in the ultraviolet to visible regions are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0153] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, hexaarylbiimidazole compound, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, and 3-arylsubstituted coumarin compound, more preferably a compound selected from oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and even more preferably an oxime compound. Furthermore, as photopolymerization initiators, the compounds described in paragraphs 0065-0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and MATERIAL STAGE Examples include peroxide-based photopolymerization initiators described in pp. 37-60, Vol. 19, No. 3, 2019; photopolymerization initiators described in International Publication No. 2018 / 221177; photopolymerization initiators described in International Publication No. 2018 / 110179; photopolymerization initiators described in Japanese Patent Publication No. 2019-043864; photopolymerization initiators described in Japanese Patent Publication No. 2019-044030; peroxide-based initiators described in Japanese Patent Publication No. 2019-167313; aminoacetophenone-based initiators having an oxazolidine group described in Japanese Patent Publication No. 2020-055992; oxime-based photopolymerization initiators described in Japanese Patent Publication No. 2013-190459; polymers described in Japanese Patent Publication No. 2020-172619; and compounds represented by Formula 1 described in International Publication No. 2020 / 152120, the contents of which are incorporated herein by reference.

[0154] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0155] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV), and Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0156] Examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in JP 2000-066385, compounds described in JP 2004-534797, compounds described in JP 2006-342166, compounds described in JP 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in JP 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, compounds described in Japanese Patent No. 5430746, and compounds described in Japanese Patent No. 5647738. Specific examples of oxime compounds include 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, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Examples of commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronley), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052).Furthermore, it is preferable to use oxime compounds that do not produce color or compounds that are highly transparent and resistant to discoloration. Examples of commercially available products include ADEKA Arclus NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

[0157] As a photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Publication No. 2014-137466, the compound described in Japanese Patent No. 6636081, and the compound described in Korean Published Patent No. 10-2016-0109444.

[0158] As a photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505.

[0159] As a photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of oxime compounds containing a fluorine atom include the compound described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852, and compound (C-3) described in Japanese Patent Publication No. 2013-164471.

[0160] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0161] Oxime compounds having a benzofuran skeleton can also be used as photopolymerization initiators. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0162] As photopolymerization initiators, oxime compounds in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019 / 088055.

[0163] Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited to these.

[0164] [ka] [ka] [ka]

[0165] The oxime compound is preferably one having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably one having a maximum absorption wavelength in the range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, even more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferable to measure it using a spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0166] As a photopolymerization initiator, it is also preferable to use a combination of Irgacure OXE01 (BASF) and / or Irgacure OXE02 (BASF) and Omnirad 2959 (IGM Resins BV).

[0167] As the photopolymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time and improving the long-term stability of the photosensitive composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include the dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. Examples include Cmpd1-7 described in Patent Publication No. 2016 / 034963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent Publication No. 6469669.

[0168] The content of the photopolymerization initiator in the total solid content of the photosensitive composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 7.5% by mass or less, and even more preferably 5% by mass or less. Only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0169] <<Solvent>> The photosensitive composition of the present invention preferably contains a solvent. Examples of solvents include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For further details, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. In addition, ester solvents and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol. Examples include monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, the amount of aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for environmental reasons (for example, it may be possible to reduce the amount to 50 ppm (parts per million) or less, 10 ppm or less, or 1 ppm or less relative to the total amount of organic solvent).

[0170] In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 ppb (parts per billion) or less by mass. If necessary, an organic solvent at the ppt (parts per trillion) level by mass may be used, and such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

[0171] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using filters. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0172] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). Furthermore, they may contain only one type of isomer or multiple types.

[0173] The peroxide content in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially peroxide-free.

[0174] The solvent content in the photosensitive composition is preferably 10 to 95% by mass. The upper limit is preferably 92.5% by mass or less, and more preferably 90% by mass or less. The lower limit is preferably 20% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, even more preferably 80% by mass or more, and particularly preferably 85% by mass or more, from the viewpoint of coatability.

[0175] Furthermore, from the viewpoint of environmental regulations, it is preferable that the photosensitive composition of the present invention substantially does not contain environmentally regulated substances. In this invention, substantially free from environmentally regulated substances means that the content of environmentally regulated substances in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are registered as environmentally regulated substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) law, and the VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly regulated. These compounds may be used as solvents when manufacturing the various components used in the photosensitive composition, and may be mixed into the photosensitive composition as residual solvents. From the viewpoint of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. One method for reducing environmentally regulated substances is to heat or reduce the pressure in the system to a temperature above the boiling point of the environmentally regulated substance, thereby removing it by distillation. Furthermore, when removing small amounts of environmentally regulated substances, azeotropic distillation with a solvent having a similar boiling point is useful to improve efficiency. Additionally, if the mixture contains compounds with radical polymerization properties, polymerization inhibitors may be added during reduced-pressure distillation to suppress the progression of radical polymerization reactions and the resulting crosslinking between molecules. These distillation methods can be implemented at any stage, including the raw material stage, the product stage (e.g., the polymerized resin solution or polyfunctional monomer solution), or the photosensitive composition stage prepared by mixing these compounds.

[0176] <<Compounds containing cyclic ether groups>> The photosensitive composition of the present invention may contain a compound having a cyclic ether group. Examples of cyclic ether groups include epoxy groups and oxetanyl groups. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).

[0177] The compound having a cyclic ether group may be a low molecular weight compound (e.g., molecular weight less than 1000) or a high molecular weight compound (macromolecule) (e.g., molecular weight of 1000 or more; in the case of a polymer, weight-average molecular weight of 1000 or more). The weight-average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight-average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0178] As compounds having a cyclic ether group, the compounds described in paragraphs 0034 to 0036 of Japanese Patent Publication No. 2013-011869, the compounds described in paragraphs 0147 to 0156 of Japanese Patent Publication No. 2014-043556, the compounds described in paragraphs 0085 to 0092 of Japanese Patent Publication No. 2014-089408, and the compounds described in Japanese Patent Publication No. 2017-179172 can also be used.

[0179] Commercially available compounds containing cyclic ether groups include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX-850 (all manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, and EPOLEAD PB. 3600, PB 4700 (all manufactured by Daicel Corporation), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (all manufactured by Daicel Corporation), jER1031S, jER157S65, jER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation), Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX (all manufactured by Toagosei Co., Ltd.), Adegaglycyrrhizol Examples include ED-505 (manufactured by ADEKA Corporation, epoxy group-containing monomer), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (all manufactured by Osaka Organic Chemical Industry Co., Ltd., oxetanyl group-containing monomer), and BATG (manufactured by Showa Denko K.K.).

[0180] The content of compounds having cyclic ether groups in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one compound having a cyclic ether group may be used, or two or more compounds may be used. When two or more compounds are used, it is preferable that their total amount is within the above range.

[0181] <<Curing accelerator>> The photosensitive composition of the present invention may contain a curing accelerator. Examples of curing accelerators include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, and onium salt compounds. Specific examples of curing accelerators include the compounds described in paragraphs 0094 to 0097 of International Publication No. 2018 / 056189, the compounds described in paragraphs 0246 to 0253 of Japanese Patent Publication No. 2015-034963, the compounds described in paragraphs 0186 to 0251 of Japanese Patent Publication No. 2013-041165, the ionic compounds described in Japanese Patent Publication No. 2014-055114, the compounds described in paragraphs 0071 to 0080 of Japanese Patent Publication No. 2012-150180, the alkoxysilane compounds having epoxy groups described in Japanese Patent Publication No. 2011-253054, the compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and the carboxyl group-containing epoxy curing agents described in Japanese Patent Publication No. 2017-036379. If a curing accelerator is included, the content of the curing accelerator in the total solid content of the photosensitive composition is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass.

[0182] <<UV absorber>> The photosensitive composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include those described in paragraphs 0038 to 0052 of Japanese Patent Publication No. 2009-217221, paragraphs 0052 to 0072 of Japanese Patent Publication No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Publication No. 2013-068814, and paragraphs 0061 to 0080 of Japanese Patent Publication No. 2016-162946, the contents of which are incorporated herein by reference. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), the Tinuvin series and Uvinul series from BASF, and the Sumisorb series from Sumika Chemtex Co., Ltd. An example of a benzotriazole compound is the MYUA series from Miyoshi Oil & Fat Co., Ltd. (Chemical Daily, February 1, 2016). Furthermore, the UV absorbers used may include compounds described in paragraphs 0049-0059 of Japanese Patent No. 6268967, compounds described in paragraphs 0059-0076 of International Publication No. 2016 / 181987, and thioaryl group-substituted benzotriazole-type UV absorbers described in International Publication No. 2020 / 137819. The content of the UV absorber in the total solid content of the photosensitive composition is preferably 0.01-10% by mass, and more preferably 0.01-5% by mass. One type of UV absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount be within the above range.

[0183] <<Polymerization inhibitor>> The photosensitive composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.). Among these, p-methoxyphenol is preferred. When a polymerization inhibitor is included, the content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.0001 to 5% by mass. There may be only one polymerization inhibitor or two or more. If there are two or more, it is preferable that the total amount is within the above range.

[0184] <<Silane coupling agent>> The photosensitive composition of the present invention may contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. A hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with amino groups, (meth)acryloyl groups, and epoxy groups being preferred. Specific examples of silane coupling agents include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503), etc. Furthermore, specific examples of silane coupling agents include the compounds described in paragraphs 0018 to 0036 of Japanese Patent Publication No. 2009-288703 and the compounds described in paragraphs 0056 to 0066 of Japanese Patent Publication No. 2009-242604, the contents of which are incorporated herein by reference. The content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.01 to 15.0% by mass, and more preferably 0.05 to 10.0% by mass. There may be only one type of silane coupling agent, or two or more types.If there are two or more types, it is preferable that the total amount falls within the above range.

[0185] <<Surfactants>> The photosensitive composition of the present invention may contain a surfactant. Various surfactants can be used, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a silicone surfactant or a fluorinated surfactant. Examples of surfactants include those described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779 and those described in Japanese Patent Application Publication No. 2020-008634, the contents of which are incorporated herein by reference.

[0186] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in photosensitive compositions.

[0187] Examples of fluorinated surfactants include those described in paragraphs 0060 to 0064 of Japanese Patent Publication No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014 / 017669), and those described in paragraphs 0117 to 0132 of Japanese Patent Publication No. 2011-132503, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, and R-01. R-40, R-40-LM, R-41, R-41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox Examples include PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futtergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218 (all manufactured by NEOS Corporation).

[0188] Furthermore, fluorinated surfactants can also suitably include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and in which the fluorine atom-containing functional group is cleaved and the fluorine atom volatilizes when heat is applied. Examples of such fluorinated surfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac DS-21.

[0189] Furthermore, it is also preferable to use a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. Examples of such fluorine-based surfactants include the fluorine-based surfactant described in Japanese Patent Application Publication No. 2016-216602, the details of which are incorporated herein by reference.

[0190] Block polymers can also be used as fluorine-based surfactants. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, fluorine-containing surfactants described in paragraphs 0016 to 0037 of Japanese Patent Application Publication No. 2010-032698, and the following compounds are also examples of fluorine-based surfactants used in the present invention. [ka] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds, the percentage indicating the proportion of repeating units is expressed as mole percent.

[0191] Furthermore, fluorinated surfactants can also be fluorinated polymers having ethylenically unsaturated bond-containing groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Publication No. 2010-164965, and Megafac RS-101, RS-102, RS-718K, RS-72-K, etc., manufactured by DIC Corporation. Additionally, fluorinated surfactants can also be compounds described in paragraphs 0015-0158 of Japanese Patent Publication No. 2015-117327.

[0192] Furthermore, using the surfactant described in International Publication No. 2020 / 084854 as a substitute for surfactants having a perfluoroalkyl group with 6 or more carbon atoms is also preferable from an environmental regulatory standpoint.

[0193] Furthermore, it is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant. [ka] In equation (fi-1), m represents 1 or 2, n represents an integer from 1 to 4, a represents 1 or 2, and X a+ This refers to α-valent metal ions, primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, quaternary ammonium ions, or NH4. + It represents.

[0194] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acids. Examples include esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0195] Examples of silicone-based surfactants include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH 8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. Examples include OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BIC Chemie), etc. In addition, compounds with the following structure can be used as silicone-based surfactants. [ka]

[0196] The surfactant content in the total solids of the photosensitive composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be of one type or two or more types. If two or more types are used, the total amount is preferably within the above range.

[0197] <<Antioxidant>> The photosensitive composition of the present invention may contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenol group and a phosphite ester group in the same molecule are also preferred as antioxidants. Phosphorus-based antioxidants can also be suitably used as antioxidants. The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. When an antioxidant is included, only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0198] <<Component B>> The photosensitive composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109, etc., of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. Furthermore, the photosensitive composition of the present invention may optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100-250°C or at 80-200°C in the presence of an acid / base catalyst, thereby removing the protecting group. Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation). Furthermore, the photosensitive composition of the present invention may also contain an aromatic group-containing phosphonium salt described in Japanese Patent Publication No. 2020-079833.

[0199] The photosensitive composition of the present invention may contain a metal oxide to adjust the refractive index of the resulting film. Examples of metal oxides include TiO2, ZrO2, Al2O3, and SiO2. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core portion may be hollow.

[0200] The photosensitive composition of the present invention may also contain a lightfastness modifier. As lightfastness modifiers, the compounds described in paragraphs 0036 to 0037 of JP 2017-198787, the compounds described in paragraphs 0029 to 0034 of JP 2017-146350, the compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of JP 2017-129774, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of JP 2017-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of JP 2017-122803, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017 / 164127, and the compounds described in paragraphs 0025 to 0039 of JP 2017-186546 Examples include the compounds described in paragraphs 0034 to 0047, the compounds described in paragraphs 0019 to 0041 of Japanese Patent Publication No. 2015-025116, the compounds described in paragraphs 0101 to 0125 of Japanese Patent Publication No. 2012-145604, the compounds described in paragraphs 0018 to 0021 of Japanese Patent Publication No. 2012-103475, the compounds described in paragraphs 0015 to 0018 of Japanese Patent Publication No. 2011-257591, the compounds described in paragraphs 0017 to 0021 of Japanese Patent Publication No. 2011-191483, the compounds described in paragraphs 0108 to 0116 of Japanese Patent Publication No. 2011-145668, and the compounds described in paragraphs 0103 to 0153 of Japanese Patent Publication No. 2011-253174.

[0201] From an environmental perspective, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. In the photosensitive composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solid content of the photosensitive composition. The photosensitive composition of the present invention may substantially not contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, a composition substantially free of perfluoroalkyl sulfonic acid and its salts may be selected. Examples of compounds that can substitute for regulated compounds include compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. The photosensitive composition of the present invention may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, to the maximum permissible extent.

[0202] The water content of the photosensitive composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably in the range of 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0203] The photosensitive composition of the present invention can be used by adjusting its viscosity for purposes such as adjusting the film surface (flatness, etc.) and adjusting the film thickness. The viscosity value can be appropriately selected as needed, but for example, 0.3 mPa·s to 50 mPa·s is preferred at 25°C, and 0.5 mPa·s to 20 mPa·s is more preferred. As a method for measuring viscosity, for example, a cone-plate type viscometer can be used and the measurement can be taken while the temperature has been adjusted to 25°C.

[0204] <<Container>> There are no particular limitations on the container used to house the photosensitive composition, and any known container can be used. Furthermore, to suppress the incorporation of impurities into the raw materials and composition, it is also preferable to use a multilayer bottle with an inner wall made of six types of resin in six layers, or a bottle with a seven-layer structure of six types of resin. An example of such a container is the container described in Japanese Patent Application Publication No. 2015-123351.

[0205] <Method for preparing a photosensitive composition> The photosensitive composition of the present invention can be prepared by mixing the aforementioned components. When preparing the photosensitive composition, all components may be dissolved and / or dispersed simultaneously in a solvent, or, if necessary, each component may be prepared as two or more solutions or dispersions and mixed at the time of use (coating) to prepare the photosensitive composition.

[0206] Furthermore, the preparation of the photosensitive composition preferably includes a process for dispersing the pigment. In the process for dispersing the pigment, examples of mechanical forces used for dispersion include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. In addition, when grinding the pigment in a sand mill (bead mill), it is preferable to process under conditions that improve grinding efficiency, such as using beads with a small diameter or increasing the bead filling rate. Furthermore, it is preferable to remove coarse particles after the grinding process by filtration, centrifugation, etc. Furthermore, the processes and dispersers for dispersing the pigments can suitably be those described in "Complete Collection of Dispersion Technology," published by Joho Kiko Co., Ltd., July 15, 2005, "Comprehensive Data Collection on Dispersion Technology and Practical Industrial Applications, Focusing on Suspension (Solid / Liquid Dispersion Systems)," published by Keiei Kaihatsu Center Publishing Department, October 10, 1978, and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, in the process of dispersing the pigments, particle refinement treatment may be performed in a salt milling step. For materials, equipment, and processing conditions used in the salt milling step, for example, refer to the descriptions in Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. As beads used for dispersion, zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof can be used. In addition, inorganic compounds with a Mohs hardness of 2 or higher can be used. The composition may contain 1 to 10,000 ppm of the above-mentioned beads.

[0207] In preparing a photosensitive composition, it is preferable to filter the composition with a filter for purposes such as removing foreign matter and reducing defects. Any filter that has been conventionally used for filtration purposes can be used without particular limitations. For example, filters made of materials such as fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight polyolefin resins) can be used. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0208] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the filter pore size is within the above range, fine foreign matter can be removed more reliably. The nominal value of the filter pore size can be referred to from the filter manufacturer. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and KITZ Microfilter Corporation can be used.

[0209] Furthermore, it is also preferable to use fibrous filter media as the filter. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) from Rokitechno Co., Ltd. When using filters, different filters (for example, a first filter and a second filter) may be combined. In this case, filtration with each filter may be performed only once or two or more times. Filters with different pore sizes within the above range may also be combined. In addition, filtration with the first filter may be performed only on the dispersion, and after mixing in other components, filtration with the second filter may be performed.

[0210] <Membrane> The film of the present invention is a film obtained from the photosensitive composition of the present invention described above. The film of the present invention can be used in color filters. More specifically, it can be preferably used in the blue pixels of a color filter. The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0211] <Color Filter> The color filter of the present invention has the film of the present invention described above. Preferably, the color filter of the present invention has the film of the present invention as the colored pixels of the color filter, and more preferably, the film of the present invention as the blue pixels. Preferably, the color filter of the present invention further includes colored pixels selected from red pixels, green pixels, cyan pixels, and yellow pixels. One embodiment of the color filter of the present invention is a color filter having blue pixels, green pixels, and red pixels composed of the film of the present invention.

[0212] The color filter of the present invention can be used in solid-state image sensors such as CCDs (charge-coupled devices) and CMOS (complementary metal-oxide-semiconductor) sensors, as well as in image display devices.

[0213] In the color filter of the present invention, the film thickness can be appropriately adjusted depending on the purpose. The film thickness is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0214] The width of the pixels included in the color filter is preferably 0.2 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. The Young's modulus of the pixels is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0215] Each pixel in the color filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. There is no lower limit, but it is preferably 0.1 nm or more. The surface roughness of the pixel can be measured using, for example, a Veeco AFM (atomic force microscope) Dimension3100. The water contact angle on the pixel can be set to a suitable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT·A (manufactured by Kyowa Interface Science Co., Ltd.). Furthermore, it is preferable that the volume resistivity of the pixel is high. Specifically, the volume resistivity of the pixel should be 10 9 It is preferable that it be Ω·cm or more, 10 11 It is more preferable that it be Ω·cm or greater. There is no upper limit specified, but for example, 10 14It is preferable that the resistance is Ω·cm or less. The volume resistivity of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest Corporation).

[0216] In color filters, a protective layer may be provided on the surface of the pixels. By providing a protective layer, various functions such as oxygen shielding, low reflectivity, hydrophilicity, and shielding of light of specific wavelengths (ultraviolet rays, near-infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Methods for forming the protective layer include applying a resin composition dissolved in an organic solvent, chemical vapor deposition, and attaching molded resin with an adhesive. The components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc. Two or more of these components may be included. For example, in the case of a protective layer intended for oxygen barrier purposes, the protective layer preferably contains polyol resin, SiO2, and Si2N4. In the case of a protective layer intended for low reflectivity purposes, the protective layer preferably contains (meth)acrylic resin and fluororesin.

[0217] When forming a protective layer by coating a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the coating method for the resin composition. The organic solvent contained in the resin composition can be a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermochemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.

[0218] The protective layer may contain additives such as organic and inorganic fine particles, light absorbers of specific wavelengths (e.g., ultraviolet, near-infrared, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic and inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium dioxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known light absorbers can be used for light absorbers of specific wavelengths. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, relative to the total mass of the protective layer.

[0219] Furthermore, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Publication No. 2017-151176 can also be used.

[0220] The color filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a grid pattern by a partition wall.

[0221] <How to manufacture color filters> Next, a method for manufacturing a color filter using the photosensitive composition of the present invention will be described. Preferably, the method for manufacturing a color filter includes the steps of: forming a photosensitive composition layer on a support using the photosensitive composition of the present invention described above; exposing the photosensitive composition layer in a patterned manner; and developing and removing the unexposed parts of the photosensitive composition layer to form a pattern (pixels). If necessary, a step of baking the photosensitive composition layer (pre-bake step) and a step of baking the developed pattern (pixels) (post-bake step) may be provided.

[0222] In the step of forming the photosensitive composition layer, the photosensitive composition of the present invention is used to form the photosensitive composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. Examples include glass substrates and silicon substrates, with silicon substrates being preferred. A charge-coupled device (CCD), complementary metal-oxide-semiconductor (CMOS), transparent conductive film, etc., may be formed on the silicon substrate. A black matrix that isolates each pixel may also be formed on the silicon substrate. Furthermore, a base layer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent diffusion of materials, or flatten the substrate surface.

[0223] Known methods can be used to coat the photosensitive composition. Examples include the drop method (drop casting); slit coating method; spray method; roll coating method; spin coating method; casting method; slit and spin method; pre-wetting method (for example, the method described in Japanese Patent Application Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand, piezo, and thermal), nozzle jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; transfer methods using molds, etc.; and nanoimprint methods. The application method for inkjet printing is not particularly limited and includes, for example, the method shown in "Expanding and Usable Inkjet Printing - Infinite Possibilities Seen in Patents," published February 2005 by Sumibe Techno Research (especially pages 115-133), as well as the methods described in Japanese Patent Publication Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-169325. Furthermore, for methods of coating the photosensitive composition, reference can be made to the descriptions in International Publication Nos. 2017 / 030174 and 2017 / 018419, and these contents are incorporated herein by reference.

[0224] The photosensitive composition layer formed on the support may be dried (pre-baked). Pre-baking is not necessary when the film is manufactured by a low-temperature process. If pre-baking is performed, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, and also 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, oven, etc.

[0225] Next, the photosensitive composition layer is exposed in a pattern (exposure step). For example, the photosensitive composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine, etc., through a mask having a predetermined mask pattern. This allows the exposed areas to be cured.

[0226] Examples of radiation (light) that can be used during exposure include g-rays and i-rays. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) 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), with KrF rays (wavelength 248 nm) being preferred. Long-wave light sources with wavelengths of 300 nm or more can also be used.

[0227] Furthermore, exposure may be performed by continuously irradiating with light, or by irradiating in pulses (pulsed exposure). Pulsed exposure is an exposure method that involves repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less).

[0228] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm². 2 Preferably, 0.05 to 1.0 J / cm² 2 This is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in air, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21 vol% (e.g., 22 vol%, 30 vol%, or 50 vol%). Furthermore, the exposure intensity can be appropriately set, usually 1000 W / m². 2 ~100,000 W / m 2 (For example, 5000W / m 2 , 15000W / m 2 , or 35000W / m 2 The oxygen concentration and exposure intensity can be combined as appropriate; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m². 2At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². 2 This can be done as follows.

[0229] Next, the unexposed areas of the photosensitive composition layer are developed and removed to form a pattern (pixels). The unexposed areas of the photosensitive composition layer can be developed and removed using a developer. This causes the unexposed areas of the photosensitive composition layer in the exposure process to dissolve in the developer, leaving only the photo-cured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve the ability to remove residue, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.

[0230] Examples of developing solutions include organic solvents and alkaline developers, with alkaline developers being preferred. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferred. Examples of alkaline agents include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, as well as inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. Alkaline agents with larger molecular weights are preferred from an environmental and safety perspective. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The developer may also contain a surfactant. Examples of surfactants include those mentioned above, and nonionic surfactants are preferred. For convenience of transport and storage, the developer may be manufactured as a concentrated solution and then diluted to the required concentration at the time of use. The dilution ratio is not particularly limited, but can be set in the range of 1.5 to 100 times, for example. It is also preferable to wash (rinse) with pure water after development. It is preferable to rinse by supplying the rinsing solution to the photosensitive composition layer after development while rotating the support on which the photosensitive composition layer has been formed after development. It is also preferable to move the nozzle that dispenses the rinsing solution from the center of the support to the periphery of the support. In this case, when moving the nozzle from the center to the periphery of the support, the speed of movement of the nozzle may be gradually reduced. By rinsing in this manner, in-plane variation of the rinse can be suppressed. Furthermore, a similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center to the periphery of the support.

[0231] After development and drying, it is preferable to perform additional exposure or heat treatment (post-bake). Additional exposure and post-bake are curing treatments after development to ensure complete hardening. The heating temperature in post-bake is preferably 100 to 240°C, and more preferably 200 to 240°C. Post-bake can be performed continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions. When performing additional exposure, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure may also be performed by the method described in Korean Published Patent No. 10-2017-0122130.

[0232] <Solid-state image sensor> The solid-state image sensor of the present invention has the film of the present invention described above. The configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor, but for example, the following configuration can be given.

[0233] The device has a substrate on which multiple photodiodes and transfer electrodes made of polysilicon or the like constitute the light-receiving area of ​​a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide-semiconductor) image sensor, etc.), a light-shielding film with an opening only for the light-receiving portion of the photodiode is placed on the photodiode and transfer electrodes, a device protection film made of silicon nitride or the like is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a color filter is placed on the device protection film. Furthermore, the device may have a configuration in which a light-gathering means (e.g., a microlens; the same applies hereinafter) is placed on the device protection film and below the color filter (on the side closer to the substrate), or a configuration in which the light-gathering means is placed on the color filter. The color filter may also have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a grid pattern. In this case, it is preferable that the partitions have a low refractive index with respect to each colored pixel. Examples of imaging devices having such a structure include those described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, and International Publication No. 2018 / 043654. Furthermore, as shown in Japanese Patent Publication No. 2019-211559, the light resistance may be improved by providing an ultraviolet absorption layer within the structure of the solid-state image sensor. The imaging device equipped with the solid-state image sensor of the present invention can be used not only in digital cameras and electronic devices with imaging functions (such as mobile phones), but also in in-vehicle cameras and surveillance cameras.

[0234] <Image display device> The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescent display devices. For definitions of image display devices and details of each image display device, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular restrictions on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology". [Examples]

[0235] The present invention will be specifically described below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, iPr represents an isopropyl group.

[0236] <Manufacturing of micronized pigments> 100 parts by mass of the pigments listed in the table below, 1200 parts by mass of sodium chloride, and 120 parts by mass of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 4 hours. The resulting kneaded composition was added to 3000 parts by mass of hot water and stirred for 1 hour to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight to obtain the finely ground pigments listed in the table below.

[0237] [Table 2]

[0238] <Manufacturing of dispersions> The mixture of raw materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.1 mm diameter). Next, a high-pressure disperser with a vacuum mechanism (NANO-3000-10, manufactured by Nippon BEE Co., Ltd.) was used to apply a pressure of 2000 kg / cm². 2 The dispersion treatment was carried out under conditions of a flow rate of 500 g / min. This dispersion treatment was repeated a total of 10 times to produce each dispersion.

[0239] [Table 3]

[0240] The details of the materials indicated by the abbreviations above are as follows:

[0241] (Finely milled pigments) Pig-1~Pig-5: The finely milled pigments Pig-1~Pig-5 mentioned above.

[0242] (Pigment derivatives) Syn-1: Compound with the following structure (blue pigment derivative. The maximum molar extinction coefficient in the wavelength range of 400-700 nm is 10,000 L·mol) -1 ·cm -1 That's all. [ka] Syn-2: Compound with the following structure (purple pigment derivative. The maximum molar extinction coefficient in the 400-700 nm wavelength range is 10,000 L·mol) -1 ·cm -1 That's all. [ka] Syn-3: Compound with the following structure (a transparent pigment derivative. The maximum molar extinction coefficient in the wavelength range of 400-700 nm is 3000 L·mol) -1 ·cm -1 below.) [ka] Syn-4: Compound with the following structure (transparent pigment derivative. Maximum molar extinction coefficient in the wavelength range of 400-700 nm is 3000 L·mol) -1 ·cm -1 below.) [ka] Syn-5: Compound with the following structure (transparent pigment derivative. Maximum molar extinction coefficient in the wavelength range of 400-700 nm is 3000 L·mol) -1 ·cm -1 below.) [ka] Syn-6: Compound with the following structure (a transparent pigment derivative; the maximum molar extinction coefficient in the wavelength range of 400-700 nm is 3000 L·mol) -1 ·cm -1 below.) [ka] Syn-7: A compound with the following structure (a transparent pigment derivative; the maximum molar extinction coefficient in the wavelength range of 400-700 nm is 3000 L·mol). -1 ·cm -1 below.) [ka]

[0243] (Dispersant) D-1: Resin with the following structure (weight-average molecular weight 20,000; the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units.) [ka] D-2: Resin with the following structure (weight-average molecular weight 800) [ka] D-3: Resin with the following structure (weight-average molecular weight 15000; the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units.) [ka] D-4: The following resin (weight-average molecular weight 8000, acid value 37 mgKOH / g, ethylenically unsaturated bond content value 0.22 mmol / g) [Table 4] [ka] [ka] [ka]

[0244] (solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Cyclopentanone S-3: Cyclohexanone

[0245] <Manufacturing of photosensitive compositions> The raw materials listed in the table below were mixed and stirred, and then filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to produce a photosensitive composition. The units of the values ​​listed in the "Amount" column are parts by mass. In addition, the total content of colorants and pigment derivatives in the total solids of each photosensitive composition is listed in the "Total Content of Colorants and Pigment Derivatives" column.

[0246] [Table 5] [Table 6]

[0247] The details of the materials indicated by the abbreviations above are as follows:

[0248] (dispersion) BB-1~BB-12, BB-c1, BB-c2: The dispersions BB-1~BB-12, BB-c1, BB-c2 mentioned above.

[0249] (dye) Dye 1: Dye with the following structure (xanthene dye, weight-average molecular weight: 9000) [ka]

[0250] (resin) B-1: Compound with the following structure (weight-average molecular weight: 11000, the values ​​appended to the main chain are molar ratios.) [ka]

[0251] (polymerizable monomer) M-1: Compound with the following structure [ka] M-2: A mixture of compounds with the following structure (a mixture in which the molar ratio of the compound on the left (a hexafunctional (meth)acrylate compound) and the compound on the right (a pentafunctional (meth)acrylate compound) is 7:3). [ka]

[0252] (Photopolymerization initiator) I-1: Compounds with the following structure [ka] I-2: Compounds with the following structure [ka] I-3: Compounds with the following structure [ka]

[0253] (Surfactants) W-1: KF-6000 (Silicone-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0254] (solvent) S-1: Propylene glycol monomethyl ether acetate

[0255] <Evaluation of lightfastness> The photosensitive composition obtained above was coated onto a 5cm x 5cm glass substrate using a spin coater to a dry film thickness of 0.6μm. It was then pre-baked at 100°C for 120 seconds using a hot plate to obtain a single-color filter for lightfastness evaluation. A 100nm thick SiO2 layer was formed on this color filter by chemical vapor deposition. A sharp-cut filter (L38, manufactured by HOYA Corporation) was placed on the obtained single-color filter for lightfastness evaluation to cut out light below 380nm, and it was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux·h). The color difference (ΔE*ab value) of the single-color filter before and after xenon lamp irradiation was measured, and the lightfastness was evaluated according to the following criteria. A smaller ΔE*ab value indicates better lightfastness. A: ΔE*ab value is less than 3 B: ΔE*ab value is 3 or greater and less than 10. C: ΔE*ab value is 10 or greater

[0256] <Evaluation of moisture resistance> The photosensitive composition obtained above was applied to a 5cm x 5cm glass substrate by spin coating to a dry film thickness of 0.6μm. It was then pre-baked at 100°C for 120 seconds using a hot plate to obtain a single-color filter for moisture resistance evaluation. A 500nm thick SiN layer was formed on this color filter by chemical vapor deposition. The obtained single-color filter for moisture resistance evaluation was left for 96 hours in an environment of 130°C and 85% humidity. The color difference (ΔE*ab value) of the color filter before and after the period of exposure was measured, and the moisture resistance was evaluated according to the following criteria. A smaller ΔE*ab value indicates better moisture resistance. A: ΔE*ab value is less than 3 B: ΔE*ab value is 3 or greater and less than 10. C: ΔE*ab value is 10 or greater

[0257] <Evaluation of storage stability> The viscosity of the photosensitive composition obtained above was measured at 25°C using an E-type viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.). After the photosensitive composition was allowed to stand at 45°C for 3 days, the viscosity was measured again. The viscosity change rate of the photosensitive composition before and after standing was calculated, and the storage stability was evaluated according to the evaluation criteria below. A smaller viscosity change rate indicates better storage stability. The viscosity of the photosensitive composition was measured under temperature-controlled conditions of 25°C. The evaluation criteria were as follows, and the evaluation results are shown in the table below. Viscosity change rate (%) = (|Viscosity of photosensitive composition after standing at 45°C for 3 days - Viscosity of photosensitive composition immediately after manufacturing| / Viscosity of photosensitive composition immediately after manufacturing) × 100 A: Viscosity change rate is less than 10% B: Viscosity change rate is 10% or more, but less than 50%. C: Viscosity change rate of 50% or more

[0258] [Table 7]

[0259] As shown in the table above, the examples showed better light resistance and moisture resistance than the comparative examples. Similar results were obtained in Example 12 when the amounts of the dispersion and resin added were changed, and the total content of the colorant and pigment derivative in the total solids was changed to 45% by mass or 50% by mass.

Claims

1. A photosensitive composition comprising a colorant A containing a pigment, a pigment derivative B, and a resin C, The aforementioned coloring agent A contains a blue pigment. The aforementioned pigment derivative B includes a transparent pigment derivative B1 and a chromatic pigment derivative B2. The pigment derivative B1 is a compound represented by formula (b1), The pigment derivative B2 is a compound having a structure in which a portion of the chromophore is replaced with an acidic or basic group, and the chromophore is a phthalocyanine skeleton or a dioxazine skeleton. A photosensitive composition wherein the total content of the coloring agent A and the pigment derivative B in the total solid content of the photosensitive composition is 40% by mass or more. A 1 -L 1 -Z 1...(b1) (In formula (b1), A1 represents a group containing a benzimidazolinone ring or a group represented by formula (A1), L1 represents a single bond or a divalent linking group. Z1 represents the group represented by formula (Z1) or the group represented by formula (Z10). 【Chemistry 1】 (In formula (A1), * represents a bond, Ya 1 and Ya 2 each independently represent -N(Ra 1)- or -O-, Ra 1 represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, or aryl group. B1 and B2 each independently represent a hydrogen atom or a substituent. 【Chemistry 2】 (In equation (Z1), * represents a bond, Yz 1 represents -N(Ry 1)- or -O-, Ry 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. Lz 1 represents a divalent linking group, Rz 1 and Rz 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. Rz 1 and Rz 2 may be bonded via a divalent group to form a ring. m represents an integer between 1 and 5. 【Transformation 3】 (In formula (Z10), * represents a bond, Lc 1 and Lc 2 each independently represent a single bond or a linking group, Rc 1 and Rc 2 each independently represent a substituent, and at least one of Rc 1 and Rc 2 represents an acidic group or a basic group.)

2. The maximum molar extinction coefficient of the pigment derivative B1 in the wavelength range of 400 to 700 nm is 3000 L·mol. －１ ・cm －１ The photosensitive composition according to claim 1, which is as follows:

3. The maximum molar extinction coefficient of the pigment derivative B2 in the wavelength range of 400 to 700 nm is 10,000 L·mol. －１ ・cm －１ The photosensitive composition according to claim 1 or 2.

4. The photosensitive composition according to claim 1 or 2, wherein A1 in formula (b1) represents a group represented by formula (A1).

5. The photosensitive composition according to claim 1 or 2, wherein the pigment derivative B2 is a phthalocyanine compound.

6. The photosensitive composition according to claim 1 or 2, wherein the maximum absorption wavelength of the pigment derivative B2 is in the range of 400 to 700 nm.

7. The photosensitive composition according to claim 1 or 2, wherein the blue pigment is a phthalocyanine compound.

8. The photosensitive composition according to claim 1 or 2, wherein the coloring agent A comprises a blue pigment and a purple pigment.

9. The photosensitive composition according to claim 1 or 2, further comprising a polymerizable monomer and a photopolymerization initiator.

10. The photosensitive composition according to claim 1 or 2, wherein when a film with a thickness of 1 μm is formed using the photosensitive composition, the average transmittance of light in the wavelength range of 400 to 500 nm in the thickness direction of the film is 55% or more, the average transmittance of light in the wavelength range of 600 to 700 nm in the thickness direction of the film is 20% or less, and the wavelength at which the transmittance is 50% exists in the wavelength range of 450 to 550 nm.

11. The photosensitive composition according to claim 1 or 2, which is a photosensitive composition for forming blue pixels.

12. A film obtained from the photosensitive composition according to claim 1 or 2.

13. A color filter having the film described in claim 12.

14. A solid-state image sensor having the film described in claim 12.

15. An image display device having the film according to claim 12.

Images