Methods for manufacturing photosensitive components, filters, and solid-state imaging elements

Abstract

This invention provides a photosensitive composition with excellent photolithography properties and capable of forming pixels with fine linewidths, a method for manufacturing a filter, and a method for manufacturing a solid-state imaging element. The photosensitive composition for exposure to light with wavelengths below 300 nm contains a colorant A, a photopolymerization initiator B, a polymerizable monomer C having groups containing vinyl unsaturated bonds, and a polymerizable resin D having groups containing vinyl unsaturated bonds. The colorant A constitutes more than 50% by mass of the total solids content of the photosensitive composition, and the polymerizable monomer C constitutes more than 4% by mass of the total solids content of the photosensitive composition. Relative to 100 parts by mass of polymerizable resin D, the composition contains 5 to 200 parts by mass of polymerizable monomer C.

Description

[Technical Field]

[0001] This invention relates to a photosensitive composition containing a colorant. More specifically, it relates to a photosensitive composition for forming a filter for a solid-state imaging element. Furthermore, this invention relates to a method for manufacturing a filter and a method for manufacturing a solid-state imaging element. [Previous Technology]

[0002] In recent years, with the popularization of digital cameras, mobile phones with cameras, etc., the demand for solid-state imaging components such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as core devices in displays or optical components.

[0003] For example, a color filter is manufactured using a photosensitive composition containing a colorant, a photopolymerization initiator, and a polymerizable monomer.

[0004] Patent Document 1 describes the following: a color filter is manufactured using a photosensitive composition, wherein the photosensitive composition contains a colorant, a photoradical polymerization initiator and a free radical polymerizable compound, and the content of the free radical polymerizable compound with a weight average molecular weight of 3000 or more in the total mass of the free radical polymerizable compound is 70% by mass or more.

[0005] [Patent Document 1] International Publication No. 2019 / 172006

[0006] In recent years, there has been ongoing efforts to miniaturize and increase the resolution of solid-state imaging devices equipped with filters such as color filters. Therefore, research is being conducted on pixel miniaturization for filters such as color filters.

[0007] Furthermore, in recent years, there has been a greater demand for miniaturization and thinning in solid-state imaging devices. Therefore, in recent years, there has been a greater demand for thinner films containing color materials, such as color filters used in solid-state imaging devices. In order to maintain the desired spectral dispersive performance and achieve thinning, it is necessary to increase the concentration of color materials in the photosensitive components used to form the film.

[0008] However, as the concentration of pigment in the total solids of the photosensitive composition increases, the proportion of components other than pigment decreases relatively, thus tending towards insufficient curing. Therefore, when forming pixels using photosensitive compositions via photolithography, there is a tendency for insufficient curing of the film when exposed through a mask, and a tendency for insufficient adhesion between the obtained pixels and the support. In particular, as the size of the mask opening narrows, the amount of exposure light illuminating the photosensitive composition to the exposure area decreases, thus failing to cure sufficiently to the bottom of the film (support side), and the resulting pixel adhesion between the obtained pixels and the support is prone to be insufficient.

[0009] While increasing the exposure during pixel formation using photolithography can sufficiently harden the film during exposure, the unexposed areas around the mask opening also harden, resulting in coarse pixel linewidths or a tendency for residue to form between pixels. Furthermore, when the mask opening size is less than 1.0 μm square, due to the effect of standing waves, the unexposed areas around the mask opening tend to harden further, and the pixel linewidth tends to be coarser than the mask opening size. This problem is particularly pronounced when the mask opening size is 0.7 μm square or less. [Summary of the Invention]

[0010] Therefore, the object of the present invention is to provide a photosensitive composition with excellent photolithography properties and capable of forming pixels with fine linewidths. Furthermore, the object of the present invention is to provide a method for manufacturing a filter and a method for manufacturing a solid-state imaging element.

[0011] According to the inventors' research, it has been found that the above-mentioned object can be achieved by setting it as follows, thus completing the present invention. Therefore, the present invention provides the following: <1> A photosensitive composition for exposure to light with a wavelength of 300 nm or less and comprising: a colorant A, a photopolymerization initiator B, a polymeric monomer C having a group containing an ethylene unsaturated bond, and a polymeric resin D having a group containing an ethylene unsaturated bond, wherein the content of the colorant A in the total solids content of the photosensitive composition is greater than 50% by mass, the content of the polymeric monomer C in the total solids content of the photosensitive composition is 4% by mass or more, and the polymeric monomer C is contained in 5 to 200 parts by mass relative to 100 parts by mass of the polymeric resin D. <2> The photosensitive composition as described in <1>, wherein the colorant A comprises a colored colorant. <3> The photosensitive composition as described in <1> or <2>, wherein the polymeric monomer C comprises a 2-8 functional polymeric monomer containing 2 to 8 groups with vinyl unsaturated bonds. <4> The photosensitive composition as described in any one of <1> to <3>, wherein the total solids content of the photosensitive composition contains 0.01 to 8 mmol / g of the polymeric monomer C. <5> The photosensitive composition as described in any one of <1> to <4>, wherein the total solids content of the photosensitive composition contains 0.001 to 5 mmol / g of the polymeric resin D. <6> The photosensitive composition as described in any one of <1> to <5>, wherein, relative to 100 parts by mass of the polymeric resin D, it contains 10 to 100 parts by mass of the polymeric monomer C. <7> A photosensitive composition as described in any one of <1> to <6>, wherein the total solids content of the photosensitive composition comprises 5 to 45% by mass of the polymeric monomer C and the polymeric resin D. <8> A photosensitive composition as described in any one of <1> to <7>, wherein the content of the photopolymerization initiator B in the total solids content of the photosensitive composition is 1 to 10% by mass. <9> A photosensitive composition as described in any one of <1> to <8>, used to form red or green pixels in a color filter. <10> A photosensitive composition as described in any one of <1> to <9>, used in a solid-state imaging element. <11> A method for manufacturing a filter, comprising: forming a photosensitive composition layer on a support using any one of <1> to <10>; exposing the photosensitive composition layer to light with a wavelength of 300 nm or less in a patterned manner; and developing to remove the unexposed portion of the photosensitive composition layer to form a pixel.<12> A method for manufacturing a filter as described in <11>, wherein the light irradiated onto the photosensitive composition layer has a wavelength of 300 nm or less and a wavelength of 248 nm. <13> A method for manufacturing a solid-state imaging element, comprising the method for manufacturing a filter as described in <11> or <12>. [Effects of the Invention].

[0012] According to the present invention, a photosensitive composition with excellent photolithography properties and capable of forming pixels with fine linewidths can be provided. Furthermore, a method for manufacturing a filter and a method for manufacturing a solid-state imaging element can be provided.

Implementation Method

[0013] Hereinafter, the contents of the present invention will be described in detail. In this specification, "~" is used to mean that the values ​​recorded before and after it are included as lower and upper limits. In the marking of groups (atomic groups) in this specification, the markings without substitution and unsubstituted include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "(meth)acrylate" means either or both of acrylate and methacrylate, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, and "(meth)acrylamide" means either or both of acrylamide and methacrylamide. In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, the weight average molecular weight and number average molecular weight are polystyrene conversion values ​​determined by GPC (gel permeation chromatography). In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition. In this specification, pigment refers to a colorant that is not easily soluble in a solvent. For example, it is preferable that the solubility of a pigment in 100g of water at 23°C and 100g of propylene glycol monomethyl ether acetate at 23°C is less than 0.1g, and more preferably less than 0.01g. In this specification, the symbols (e.g., A, B, C, and D) preceding or following the name are used to distinguish the constituent elements and do not limit the type, quantity, or quality of the constituent elements. In this specification, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps, as long as the expected effect of the step is achieved.

[0014] <Photosensitive Composition> The photosensitive composition of the present invention is used for exposure to light with a wavelength of less than 300 nm and contains: a colorant A, a photopolymerization initiator B, a polymerizable monomer C having a group containing an ethylene unsaturated bond, and a polymerizable resin D having a group containing an ethylene unsaturated bond. The colorant A has a content of more than 50% by mass in the total solids content of the photosensitive composition, and the polymerizable monomer C has a content of more than 4% by mass in the total solids content of the photosensitive composition. Relative to 100 parts by mass of polymerizable resin D, it contains 5 to 200 parts by mass of polymerizable monomer C.

[0015] According to the photosensitive composition of the present invention, although the content of the colorant in the total solids is greater than 50% by mass, the photolithography properties are also excellent, and it is possible to form pixels with fine linewidths (e.g., linewidth less than 1.0 μm, preferably less than 0.7 μm, more preferably less than 0.6 μm). The detailed reasons for obtaining such effects are not yet clear, but are speculated as follows.

[0016] The photosensitive composition of the present invention is a photosensitive composition for exposure under light with a wavelength of 300 nm or less. Since light with a wavelength of 300 nm or less is light with high energy density, by irradiating the photosensitive composition of the present invention with light with a wavelength of 300 nm or less, a large number of active species such as free radicals can be instantaneously generated from the photopolymerization initiator in the exposure section. By utilizing the instantaneous generation of a large number of active species such as free radicals in the exposure section to suppress the deactivation caused by oxygen, the polymerizable monomer, polymerizable resin, etc., can be effectively hardened. Therefore, although the detailed reasons are not clear, it is speculated that in the photosensitive composition of the present invention, by having a polymerizable monomer C content of 4% by mass or more in the total solids of the photosensitive composition and containing 5 to 200 parts by mass of polymerizable monomer C relative to 100 parts by mass of polymerizable resin D, the hardening of the non-exposed area at the periphery of the mask during exposure can be suppressed, and pixels with fine linewidths can be formed.

[0017] The photosensitive composition of the present invention is a photosensitive composition for exposure to light with a wavelength of 300 nm or less. The light used for exposure is preferably light with a wavelength of 180 to 300 nm. Specifically, examples include light with a wavelength of 248 nm (KrF rays) and light with a wavelength of 193 nm (ArF rays), with light with a wavelength of 248 nm (KrF rays) being preferred.

[0018] The base value (hereinafter also referred to as C=C value) of the vinyl unsaturated bond contained in the polymeric monomer C in the total solids content of the photosensitive composition of the present invention is preferably 0.01 to 8 mmol / g. The lower limit is preferably 0.05 mmol / g or more, and more preferably 0.1 mmol / g or more. The upper limit is preferably 4 mmol / g or less, and more preferably 2.5 mmol / g or less. As long as the C=C value of the polymeric monomer C in the total solids content of the photosensitive composition is within the above range, high-density three-dimensional cross-linking can be formed by exposure, and fine patterning is effective. In addition, the C=C value of the polymeric monomer C in the total solids content of the photosensitive composition refers to the sum of the products of the content of each polymeric monomer and the C=C value of each polymeric monomer in the total solids content of the photosensitive composition, divided by the total solids content of the photosensitive composition. Furthermore, the C=C value of a polymerizable monomer is calculated by dividing the number of groups containing vinyl unsaturated bonds in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

[0019] The C=C value of the total solids content of the photosensitive composition of the present invention derived from polymeric resin D is preferably 0.001 to 5 mmol / g. The lower limit is preferably 0.005 mmol / g or more, and more preferably 0.01 mmol / g or more. The upper limit is preferably 3 mmol / g or less, and more preferably 1 mmol / g or less. As long as the C=C value of the total solids content of the photosensitive composition derived from polymeric resin D is within the above range, a high molecular weight polymer can be formed by exposure, and pixels with fine linewidths and excellent adhesion to the support can be formed. Furthermore, the C=C value of the total solids content of the photosensitive composition derived from polymeric resin D refers to the sum of the products of the content of each polymeric resin and the C=C value of each polymeric resin in the total solids content of the photosensitive composition, divided by the total amount of the photosensitive composition. Furthermore, the C=C value of a polymeric resin refers to the molar amount of C=C groups per 1g of solid component of the polymeric resin. The C=C value of a polymeric resin can be calculated as follows: The low molecular weight component (a) at the C=C group site is extracted from the polymeric resin by alkali treatment, and the content of the low molecular weight component (a) relative to the C=C group site of the polymeric resin is determined by high performance liquid chromatography (HPLC), calculated using the following formula. Alternatively, when the C=C group site cannot be extracted from the polymeric resin by alkali treatment, the value determined by NMR (nuclear magnetic resonance) is used. The C=C value of the polymeric resin [mmol / g] = (Content of low molecular weight component (a) [ppm] / Molecular weight of low molecular weight component (a) [g / mol]) × 10³

[0020] The C=C value of the solid component of the photosensitive composition of the present invention is preferably 0.01 to 10 mmol / g. The lower limit is preferably 0.05 mmol / g or more, and more preferably 0.1 mmol / g or more. The upper limit is preferably 5 mmol / g or less, and more preferably 3 mmol / g or less. As long as the C=C value of the solid component of the photosensitive composition is within the above range, the difference in alkaline developability between the exposed and unexposed areas is effectively amplified due to excellent curing properties, thus effectively enabling fine patterning. Furthermore, the C=C value of the solid component of the photosensitive composition refers to the molar amount of C=C groups per 1g of solid component of the photosensitive composition. The C=C value of the solid component of the photosensitive composition can be calculated as follows: The low molecular weight component (a) at the C=C group is extracted from the solid component of the photosensitive composition by alkali treatment, and the content of the low molecular weight component (a) at the C=C group relative to the solid component of the photosensitive composition is determined by high performance liquid chromatography (HPLC), and calculated using the following formula. Alternatively, if the C=C group cannot be extracted from the solid component of the photosensitive composition by alkali treatment, the value determined by NMR (nuclear magnetic resonance) is used. The C=C value of the solid component of the photosensitive composition [mmol / g] = (content of low molecular weight component (a) [ppm] / molecular weight of low molecular weight component (a) [g / mol]) × 10³

[0021] The photosensitive composition of the present invention can be preferably used as a photosensitive composition for a filter. Examples of filters include color filters, near-infrared cut-off filters, and near-infrared transmittance filters, with color filters being preferred.

[0022] As a color filter, a filter having colored pixels can be cited as an example. As colored pixels, examples include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc.

[0023] As a near-infrared cutoff filter, a filter that blocks at least a portion of the wavelengths of light in the near-infrared region can be cited. It is preferable that the maximum absorption wavelength of the near-infrared cutoff filter is in the wavelength range of 700–1800 nm, more preferably in the wavelength range of 700–1300 nm, and even more preferably in the wavelength range of 700–1000 nm. Furthermore, it is preferable that the transmittance of the near-infrared cutoff filter is 70% or more in all wavelength ranges from 400 to 650 nm, more preferably 80% or more, and even more preferably 90% or more. Furthermore, it is preferable that the transmittance at at least one point in the wavelength range of 700–1800 nm is 20% or less. Furthermore, for near-infrared cutoff filters, a ratio of absorbance Amax at the maximum absorption wavelength to absorbance A550 at 550 nm (absorbance Amax / absorbance A550) of 20 to 500 is preferred, 50 to 500 is even better, 70 to 450 is further preferred, and 100 to 400 is particularly preferred.

[0024] As a near-infrared transmission filter, a filter that blocks at least a portion of visible light while allowing at least a portion of near-infrared light to pass through can be cited. Specific examples of near-infrared transmission filters include filters that satisfy the following spectral characteristics: a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400–640 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100–1300 nm. It is preferable that the near-infrared transmission filter satisfies any one of the following spectral characteristics (IR1) to (IR5). (IR1): A filter whose maximum transmittance is 20% or less (preferably 15% or less, more preferably 10%) in the wavelength range of 400–640 nm and whose minimum transmittance is 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800–1500 nm. (IR2): A filter whose maximum transmittance is 20% or less (preferably 15% or less, more preferably 10%) in the wavelength range of 400–750 nm and whose minimum transmittance is 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900–1500 nm. (IR3): A filter whose maximum transmittance in the wavelength range of 400–830 nm is 20% or less (preferably 15% or less, more preferably 10%) and whose minimum transmittance in the wavelength range of 1000–1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (IR4): A filter whose maximum transmittance in the wavelength range of 400–950 nm is 20% or less (preferably 15% or less, more preferably 10%) and whose minimum transmittance in the wavelength range of 1100–1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (IR5): A filter whose maximum transmittance in the wavelength range of 400 to 1050 nm is less than 20% (preferably less than 15%, more preferably less than 10%) and whose minimum transmittance in the wavelength range of 1200 to 1500 nm is more than 70% (preferably more than 75%, more preferably more than 80%).

[0025] The photosensitive composition of the present invention is preferably used as a photosensitive composition for forming colored pixels of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, with red pixels or green pixels being preferred. Furthermore, the photosensitive composition of the present invention is preferably used as a photosensitive composition for solid-state imaging devices. More specifically, it is preferably used as a photosensitive composition for filters of solid-state imaging devices, more preferably as a photosensitive composition for forming colored pixels of color filters of solid-state imaging devices, and particularly preferably as a photosensitive composition for forming red or green pixels of color filters of solid-state imaging devices. The colored pixels of the color filter can be formed using a photosensitive composition containing a colored pigment.

[0026] The concentration of the solid component 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.

[0027] Hereinafter, the components of the photosensitive composition used in the present invention will be described.

[0028] <<Color Material>> The photosensitive composition of the present invention contains a color material A (hereinafter referred to as the color material). The color material can be a pigment or a dye. Pigments and dyes can be used simultaneously. Furthermore, the pigment can be any one of inorganic pigments or organic pigments. Furthermore, the pigment can also be a material in which a portion of an inorganic pigment or an organic-inorganic pigment is replaced with an organic chromophore. By replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, hue design can be easily performed.

[0029] The average primary particle size of the pigment is preferably 1 to 200 nm. A lower limit of 5 nm or more is preferred, and 10 nm or more is even more preferred. An upper limit of 180 nm or less is preferred, 150 nm or less is even more preferred, and 100 nm or less is even more preferred. As long as the average primary particle size of the pigment is within the above range, the dispersion stability of the pigment in the photosensitive composition is good. Furthermore, in this invention, the primary particle size of the pigment can be determined by observing the primary particles of the pigment using a transmission electron microscope and based on the obtained image photograph. Specifically, the projected area of ​​the primary particles of the pigment is calculated, and the corresponding equivalent circle diameter is calculated as the primary particle size of the pigment. Also, the average primary particle size in this invention is set as the arithmetic mean of the primary particle sizes of 400 pigment particles. Furthermore, the primary particles of the pigment refer to unaggregated independent particles.

[0030] It is preferable to use color materials containing pigments. It is preferable for the pigment content in the color material to be 50% by mass or more, even better if it is 70% by mass or more, further better if it is 80% by mass or more, and especially better if it is 90% by mass or more.

[0031] Types of color materials include colored color materials, black color materials, white color materials, and near-infrared absorbing color materials, with colored color materials being preferred. Furthermore, pigments (colored pigments) are preferred among the colored color materials. Photosensitive compositions containing colored color materials are better suited for use as photosensitive compositions for forming colored pixels in color filters.

[0032] (Colored material) As a colored material, examples include colored materials that have a large absorption wavelength in the wavelength range of 400 to 700 nm. For example, examples include yellow, orange, red, green, purple, and blue colored materials. Specific examples of colored materials include those shown below.

[0033] Colorimetric Index (CI) Pigment 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, 126, 12 Yellow pigments in the following series: 7, 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 (methylene series), 233 (quinoline series), 234 (aminoketone series), 235 (aminoketone series), 236 (aminoketone series). CI pigments include 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.) and 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 (Organo Ultramarine, Bluish Red), 295 (Monoazo), 296 (Diazo), 297 (Kamaketone), etc., are red pigments.CI pigments include: Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine), 65 (phthalocyanine), 66 (phthalocyanine), etc. CI pigments include: Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane), 61 (azophosphorus), etc. CI pigments include: Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo), 88 (methylene), etc.

[0034] Furthermore, as a green pigment, zinc halide phthalocyanine pigments with an average number of halogen atoms of 10 to 14, bromine atoms of 8 to 12, and chlorine atoms of 2 to 5 per molecule can also be used. As a specific example, the compound described in International Publication No. 2015 / 118720 can be cited. Furthermore, as a green pigment, it can also use compounds described in Chinese Patent Application No. 106909027, phthalocyanine compounds with phosphate esters as ligands described in International Publication No. 2012 / 102395, phthalocyanine compounds described in Japanese Patent Application Publication No. 2019-008014, phthalocyanine compounds described in Japanese Patent Application Publication No. 2018-180023, compounds described in Japanese Patent Application Publication No. 2019-038958, and core-shell pigments described in Japanese Patent Application Publication No. 2020-076995, etc.

[0035] Furthermore, aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue pigments. Specific examples include the compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Application Publication No. 2011-157478.

[0036] Furthermore, nickel azobarbiturate complexes with the following structure can also be used as yellow pigments. [Chemical Formula 1]

[0037] As a red pigment, it is also possible to use diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in Japanese Patent Application Publication No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, and naphthol described in Japanese Patent Application Publication No. 2012-229344. Azo compounds, red pigments described in Japanese Patent No. 6516119, red pigments described in Japanese Patent No. 6525101, diketonepyrrolopyrrole compounds described in paragraph 0229 of Japanese Patent Application Publication No. 2020-090632, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, and perylene compounds described in Japanese Patent Application Publication No. 2020-079396, etc. Furthermore, as red pigments, compounds having the following structure can also be used: aromatic cyclic groups with bonded oxygen, sulfur, or nitrogen atoms introduced into the aromatic ring are bonded to the diketonepyrrolopyrrole skeleton.

[0038] Furthermore, as a yellow pigment, compounds described in Japanese Patent Application Publication No. 2017-201003, Japanese Patent Application Publication No. 2017-197719, compounds described in paragraphs 0011-0062, 0137-0276 of Japanese Patent Application Publication No. 2017-171912, compounds described in paragraphs 0010-0062, 0138-0295 of Japanese Patent Application Publication No. 2017-171913, compounds described in paragraphs 0011-0062, 0139-0190 of Japanese Patent Application Publication No. 2017-171914, and compounds described in paragraphs 0010-0065 of Japanese Patent Application Publication No. 2017-171915 are also applicable. The compounds described in paragraphs 0142 to 0222, the quinoline yellow compounds described in paragraphs 0011 to 0034 of Japanese Patent Application Publication No. 2013-054339, the quinoline yellow compounds described in paragraphs 0013 to 0058 of Japanese Patent Application Publication No. 2014-026228, the isoindoline compounds described in Japanese Patent Application Publication No. 2018-062644, the quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-203798, the quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-062578, the quinoline yellow compounds described in Japanese Patent Application Publication No. 6432077, the quinoline yellow compounds described in Japanese Patent Application Publication No. 6432076, and the Japanese Patent Application Publication No. 6432076. The quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-155881, Japanese Patent Application Publication No. 2018-111757, Japanese Patent Application Publication No. 2018-040835, Japanese Patent Application Publication No. 2017-197640, Japanese Patent Application Publication No. 2016-145282, Japanese Patent Application Publication No. 2014-085565, Japanese Patent Application Publication No. 2014-021139, Japanese Patent Application Publication No. 2013-209614, and Japanese Patent Application Publication No. 2013-209435. The quinoline yellow compounds described in the following publications: Japanese Patent Application Publication No. 2013-181015, Japanese Patent Application Publication No. 2013-061622, Japanese Patent Application Publication No. 2013-054339, Japanese Patent Application Publication No. 2013-032486, Japanese Patent Application Publication No. 2012-226110, Japanese Patent Application Publication No. 2008-074987, Japanese Patent Application Publication No. 2008-081565, and Japanese Patent Application Publication No. 2008-074986.The following compounds are described in Japanese Patent Application Publication No. 2008-074985, Japanese Patent Application Publication No. 2008-050420, Japanese Patent Application Publication No. 2008-031281, Japanese Patent Publication No. 48-032765, Japanese Patent Application Publication No. 2019-008014, Korean Patent Publication No. 10-2014-0034963, Japanese Patent Application Publication No. 2017-095706, Taiwan Patent Application Publication No. 201920495, and Japanese Patent Publication No. 6607427. Furthermore, from the viewpoint of improving color value, polymerizing these compounds is also preferable. Furthermore, as a yellow pigment, compounds represented by formula (QP1) and compounds represented by formula (QP2) can also be used. [Chemical Formula 2]

[0039] In formula (QP1), X1 to X16 each independently represent a hydrogen atom or a halogen atom, and Z1 represents an alkyl group having 1 to 3 carbon atoms. As a specific example of a compound represented by formula (QP1), the compound described in paragraph 0016 of Japanese Patent No. 6443711 can be cited. [Chemical Formula 3]

[0040] In formula (QP2), Y1 to Y3 each independently represent halogen atoms. n and m represent integers from 0 to 6, and p represents integers from 0 to 5. (n+m) is 1 or more. As a specific example of a compound represented by formula (QP2), the compound described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077 can be cited.

[0041] Furthermore, as a colorant, the diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used.

[0042] Regarding the optimal diffraction angle of various pigments, reference can be made to the records in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, and Japanese Unexamined Patent Application Publication No. 2020-026503, the contents of which are incorporated herein by reference.

[0043] Furthermore, dyes can also be used as coloring materials. There are no particular restrictions on the dyes used; known dyes can be used. Examples include pyrazolium azo compounds, aniline azo compounds, triarylmethane compounds, anthraquinone compounds, anthracene pyridine compounds, benzylene compounds, oxacyanine compounds, pyrazolotriazole azo compounds, pyridone azo compounds, anthocyanin compounds, phenanthrene compounds, pyrrolopyrazolium azomethine compounds, phthalocyanine compounds, benzo[a]piperanone compounds, indigo compounds, and pyrrolemethylene compounds. Furthermore, pigment polymers can also be used as dyes. Pigment polymer systems having two or more pigment structures per molecule are preferred, especially three or more pigment structures. There is no particular upper limit; it can be set to 100 or less. The multiple pigment structures in a molecule can be the same pigment structure or different pigment structures. The weight-average molecular weight (Mw) of the pigment polymer is preferably between 2000 and 50000. A lower limit of 3000 or above is preferred, and 6000 or above is even more preferred. An upper limit of 30000 or below is preferred, and 20000 or below is even more preferred. The pigment polymer can also be compounds described in Japanese Patent Application Publication No. 2011-213925, Japanese Patent Application Publication No. 2013-041097, Japanese Patent Application Publication No. 2015-028144, Japanese Patent Application Publication No. 2015-030742, Japanese Patent Application Publication No. 2016-102191, and International Publication No. 2016 / 031442.

[0044] Two or more color pigments can also be used in combination. For example, when the photosensitive composition of the present invention is used to form the green pixel of a color filter, it is preferable to use both green and yellow pigments. Furthermore, regarding the ratio of green to yellow pigments, it is preferable that the yellow pigment is 15 to 100 parts by weight relative to 100 parts by weight of green pigment, more preferably 20 to 70 parts by weight, and further preferably 25 to 60 parts by weight. It is preferable that the green pigment is CI pigment green 7, 36, 58, 59, or 63, and more preferably CI pigment green 36 or 58. It is preferable that the yellow pigment is CI pigment yellow 129, 138, 139, 150, 185, 215, 231, or 233, and more preferably CI pigment yellow 129, 139, 185, or 215.

[0045] Furthermore, when the photosensitive composition of the present invention is used to form the red pixel of a color filter, it is preferable to use both red and yellow pigments. Also, regarding the ratio of red to yellow pigments, it is preferable that the yellow pigment is 20-70 parts by weight relative to 100 parts by weight of red pigment, more preferably 25-60 parts by weight, and further preferably 30-50 parts by weight. It is preferable that the red pigments are CIP pigment reds 177, 254, 264, 269, 272, 291, 296, and 297, and more preferably CI pigment reds 177, 254, 264, 269, and 272. It is preferable that the yellow pigments are CI pigment yellows 129, 138, 139, 150, 185, 215, 231, and 233, more preferably CI pigment yellows 139, 185, and 215, and further preferably CI pigment yellow 139.

[0046] Furthermore, when two or more colored pigments are used in combination, black can be formed by combining the two or more colored pigments. Examples of such combinations include the following (Bk1) to (Bk7). When a photosensitive composition contains two or more colored pigments, and black is presented by combining the two or more colored pigments, such a photosensitive composition can be better used as a photosensitive composition for forming near-infrared transmission filters. (Bk1) A composition containing red and blue pigments. (Bk2) A composition containing red, blue, and yellow pigments. (Bk3) A composition containing red, blue, yellow, and purple pigments. (Bk4) A composition containing red, blue, yellow, purple, and green pigments. (Bk5) A composition containing red, blue, yellow, and green pigments. (Bk6) Contains red, blue, and green pigments. (Bk7) Contains yellow and purple pigments.

[0047] (White Pigment) Examples of white pigments include titanium dioxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide, among other inorganic pigments (white pigments). White pigments containing titanium atoms are preferred, with titanium dioxide being even more preferred. Furthermore, white pigments with a refractive index of 2.10 or higher for light with a wavelength of 589 nm are preferred. A refractive index of 2.10 to 3.00 is preferred, and 2.50 to 2.75 is even more preferred. Additionally, the white pigment can also be titanium dioxide as described in "Titanium Dioxide Properties and Application Technology, Kiyono Kagaku, pp. 13-45, published June 25, 1991, Gihodo Publishing".

[0048] White pigments can be made not only of a single inorganic substance, but also of particles combined with other materials. For example, it is preferable to use particles with internal pores, particles of other materials, particles with a core particle to which a plurality of inorganic particles are attached, or core-shell composite particles consisting of a core particle composed of polymer particles and a shell composed of inorganic nanoparticles. As for core-shell composite particles consisting of a core particle composed of the aforementioned polymer particles and a shell composed of inorganic nanoparticles, for example, reference can be made to paragraphs 0012 to 0042 of Japanese Patent Application Publication No. 2015-047520, the contents of which are incorporated herein by reference.

[0049] Hollow inorganic particles can also be used for white pigments. Hollow inorganic particles refer to inorganic particles with a hollow structure inside, and specifically to inorganic particles with cavities surrounded by an outer shell. Examples of hollow inorganic particles include those described in Japanese Patent Application Publication No. 2011-075786, International Publication No. 2013 / 061621, and Japanese Patent Application Publication No. 2015-164881, the contents of which are incorporated herein by reference.

[0050] (Black Pigment Material) There are no particular limitations on the black pigment material, and known materials can be used. For example, as an inorganic black pigment material, carbon black, titanium black, and graphite can be mentioned, with carbon black and titanium black being preferred, and titanium black being even more preferred. Titanium black refers to black particles containing titanium atoms, with low-order titanium oxide and titanium oxynitride being preferred. Titanium black can be surface-modified as needed to improve dispersibility and suppress agglomeration. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Furthermore, it can also be treated with water-repellent substances as shown in Japanese Patent Application Publication No. 2007-302836. As a black pigment material, pigment black with colorimetric index (CI) of 1 and 7 can be mentioned. Regarding titanium black, it is preferable that the primary particle size and average primary particle size of each particle are small. Specifically, an average primary particle size of 10 to 45 nm is preferred. Titanium black can also be used as a dispersion. For example, dispersions containing titanium black particles and silicon dioxide particles, wherein the ratio of Si atoms to Ti atoms in the dispersion is adjusted to be in the range of 0.20 to 0.50, etc. Regarding the above-mentioned dispersions, please refer to paragraphs 0020 to 0105 of Japanese Patent Application Publication No. 2012-169556, the contents of which are incorporated herein by reference. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (manufactured by Mitsubishi Materials Corporation), and Tilack D (manufactured by Ako Kasei Co., Ltd.). Examples of organic black pigments include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. Examples of bisbenzofuranone compounds include those described in Japanese Patent Application Publication Nos. 2010-534726, 2012-515233, 2012-515234, International Publication No. 2014 / 208348, and 2015-525260, which can be obtained, for example, as "Irgaphor Black" manufactured by BASF. Examples of perylene compounds include CI Pigment Black 31 and 32. Examples of azomethine compounds include those described in Japanese Patent Application Publication Nos. 01-170601 and 02-034664, which can be obtained, for example, as "CHROMO FINE BLACK A1103" manufactured by Dainichiseika Color & Chemicals Mfg.Co.,Ltd. Furthermore, as an organic black pigment, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of Japanese Patent Application Publication No. 2017-226821 can be used.

[0051] (Near-infrared absorbing colorant) Near-infrared absorbing colorant is preferably a pigment, and organic pigment is more preferred. Furthermore, near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the range of wavelengths greater than 700 nm and less than 1400 nm. Moreover, the maximum absorption wavelength of the near-infrared absorbing colorant is preferably less than 1200 nm, more preferably less than 1000 nm, and further preferably less than 950 nm. Furthermore, the ratio of the absorbance A550 at a wavelength of 550 nm to the absorbance Amax at the maximum absorption wavelength, i.e., A550 / Amax, is preferably less than 0.1, more preferably less than 0.05, further preferably less than 0.03, and particularly preferably less than 0.02. The lower limit is not particularly limited; for example, it can be set to 0.0001 or more, or 0.0005 or more. As long as the ratio of the above absorbance is within the above range, it can be used as a near-infrared absorbing color material with excellent visible transparency and near-infrared shielding properties. In addition, the values ​​of the maximum absorption wavelength and the absorbance at each wavelength of the near-infrared absorbing color material are obtained by measuring the absorption spectrum of the film formed using a photosensitive composition containing the near-infrared absorbing color material.

[0052] As a near-infrared absorbing colorant, there are no particular limitations, and examples include pyrrolopyrrole compounds, anthocyanin compounds, squaric acid cyanide compounds, phthalocyanine compounds, naphthalene phthalocyanine compounds, quaterrylene compounds, anthocyanin compounds, ketoneonium compounds, oxacyanine compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, and dithioene metal complexes. Examples of pyrrolopyrrole compounds include those described in paragraphs 0016 to 0058 of Japanese Patent Application Publication No. 2009-263614, those described in paragraphs 0037 to 0052 of Japanese Patent Application Publication No. 2011-068731, and those described in paragraphs 0010 to 0033 of International Patent Application Publication No. 2015 / 166873. Examples of compounds that can be cited as squaric acid cyanine compounds include those described in paragraphs 0044 to 0049 of Japanese Patent Application Publication No. 2011-208101, those described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 6065169, those described in paragraph 0040 of International Publication No. 2016 / 181987, those described in Japanese Patent Application Publication No. 2015-176046, and those described in paragraph 0072 of International Publication No. 2016 / 190162. Compounds described in paragraphs 0196 to 0228 of Japanese Patent Application Publication No. 2016-074649, compounds described in paragraph 0124 of Japanese Patent Application Publication No. 2017-067963, compounds described in International Publication No. 2017 / 135359, compounds described in Japanese Patent Application Publication No. 2017-114956, compounds described in Japanese Patent Publication No. 6197940, and compounds described in International Publication No. 2016 / 120166, etc. Examples of anthocyanin compounds include those described in paragraphs 0044-0045 of Japanese Patent Application Publication No. 2009-108267, those described in paragraphs 0026-0030 of Japanese Patent Application Publication No. 2002-194040, those described in Japanese Patent Application Publication No. 2015-172004, those described in Japanese Patent Application Publication No. 2015-172102, those described in Japanese Patent Application Publication No. 2008-088426, those described in paragraph 0090 of International Patent Application Publication No. 2016 / 190162, and those described in Japanese Patent Application Publication No. 2017-031394. Examples of ketoneon compounds include those described in Japanese Patent Application Publication No. 2017-082029.Examples of ammonium compounds include those described in Japanese Patent Publication No. 2008-528706, Japanese Patent Application Publication No. 2012-012399, Japanese Patent Application Publication No. 2007-092060, and International Patent Publication No. 2018 / 043564, paragraphs 0048 to 0063. Examples of phthalocyanine compounds include those described in Japanese Patent Application Publication No. 2012-077153, paragraph 0093, Japanese Patent Application Publication No. 2006-343631, Japanese Patent Application Publication No. 2013-195480, Japanese Patent Application Publication No. 6081771, and International Patent Publication No. 2020 / 071470. As a naphthalene phthalocyanine compound, the compound described in paragraph 0093 of Japanese Patent Application Publication No. 2012-077153 can be cited. As a dithioene metal complex, the compound described in Japanese Patent Publication No. 5733804 can be cited.

[0053] As a near-infrared absorbing color material, the following compounds can also be used: sulforaphane compounds described in Japanese Patent Application Publication No. 2017-197437, Japanese Patent Application Publication No. 2017-025311, International Publication No. 2016 / 154782, Japanese Patent No. 5884953, and Japanese Patent No. 6036689. Squamarine compounds, squamarine compounds described in Japanese Patent No. 5810604, squamarine compounds described in paragraphs 0090-0107 of International Publication No. 2017 / 213047, pyrrole ring-containing compounds described in paragraphs 0019-0075 of Japanese Patent Application Publication No. 2018-054760, and pyrrole ring-containing compounds described in paragraphs 0078-0082 of Japanese Patent Application Publication No. 2018-040955. The following compounds contain pyrrole rings as described in paragraphs 0043 to 0069 of Japanese Patent Application Publication No. 2018-002773; the squaric acid compounds having an aromatic ring at the α-position of acetylamine as described in paragraphs 0024 to 0086 of Japanese Patent Application Publication No. 2018-041047; the acetylamine-linked squaric acid compounds as described in Japanese Patent Application Publication No. 2017-179131; and the compounds containing pyrrole rings as described in Japanese Patent Application Publication No. 2017-141215. Compounds with a squaric acid cyanine skeleton or a ketone cyanine skeleton, dihydrocarbazole bisquaric acid cyanine compounds described in Japanese Patent Application Publication No. 2017-082029, asymmetric compounds described in paragraphs 0027 to 0114 of Japanese Patent Application Publication No. 2017-068120, pyrrole ring-containing compounds (carbazole type) described in Japanese Patent Application Publication No. 2017-067963, and phthalocyanine compounds described in Japanese Patent No. 6251530, etc.

[0054] The content of the colorant in the total solids of the photosensitive composition is more than 50% by mass, preferably 51% by mass or more, more preferably 53% by mass or more, and even more preferably 55% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0055] Furthermore, the content of the colorant is preferably 200 to 2000 parts by mass relative to 100 parts by mass of the polymeric monomer. The lower limit is preferably 250 parts by mass or more, more preferably 300 parts by mass or more, and even more preferably 350 parts by mass or more. The upper limit is preferably 1500 parts by mass or less, more preferably 1200 parts by mass or less, even more preferably 800 parts by mass or less, and particularly preferably 600 parts by mass or less.

[0056] Furthermore, the content of colorant is preferably 100 to 1500 parts by weight relative to 100 parts by weight of polymeric resin. The lower limit is preferably 150 parts by weight or more, and more than 200 parts by weight. The upper limit is preferably 1200 parts by weight or less, more than 1000 parts by weight, and even more preferably 500 parts by weight or less.

[0057] <<Photopolymerization Initiator>> The photosensitive composition of the present invention contains photopolymerization initiator B (hereinafter referred to as photopolymerization initiator). There are no particular limitations on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitive to light in the ultraviolet to visible regions are preferred. Photopolymerization initiator is preferably a photoradical polymerization initiator.

[0058] As photopolymerization initiators, examples include halogenated hydrocarbon derivatives (e.g., compounds with a trihalomethane skeleton, compounds with an oxadiazole skeleton, etc.), acetyphosphine compounds, hexaaryl biimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, etc. From the perspective of exposure sensitivity, photopolymerization initiators are preferably trihalomethane trihalomethane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetophosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onmium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. Compounds selected from oxime compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and acetophosphine compounds are more preferred, with oxime compounds being even more preferred. Furthermore, as photopolymerization initiators, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent Application Publication No. 6301489, and MATERIAL STAGE. Peroxide-based photopolymerization initiators described in 37-60p, 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 Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, aminoacetophenone-based initiators with oxazolidinyl groups described in Japanese Patent Application Publication No. 2020-055992, and oxime-based photopolymerization initiators described in Japanese Patent Application Publication No. 2013-190459 are all included in this specification.

[0059] Examples of commercially available α-hydroxy ketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Examples of commercially available α-amino ketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acetylsphine compounds include Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (both manufactured by BASF).

[0060] Examples of oxime compounds include those described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, JCS Perkin II (1979, pp. 1653-1660), JCS Perkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and... Compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Application Publication No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc. Specific examples of oxime compounds include 3-benzoxyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propoxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoxyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonoxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Commercially available examples include Irgacure-OXE01, Irgacure-OXE02, Irgacure-OXE03, and Irgacure-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), and Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, as described in Japanese Patent Application Publication No. 2012-014052, a photopolymerization initiator 2). Furthermore, as oxime compounds, compounds that are colorless or highly transparent and resistant to discoloration are preferred. Commercially available examples include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0061] Oxime compounds having a cyclohexane ring can also be used as photopolymerization initiators. Specific examples of oxime compounds having a cyclohexane ring include the compound described in Japanese Patent Application Publication No. 2014-137466, the compound described in Japanese Patent Publication No. 6636081, and the compound described in Korean Patent Publication No. 10-2016-0109444.

[0062] As a photopolymerization initiator, an oxime compound having at least one benzene ring having a carbazole ring as the backbone of a naphthalene ring can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505.

[0063] Oxime compounds having fluorine atoms can also be used as photopolymerization initiators. Specific examples of oxime compounds having fluorine atoms include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in Japanese Patent Application Publication No. 2013-164471.

[0064] As a photopolymerization initiator, a nitro oxime compound can be used. It is also preferable that the nitro oxime compound is a dimer. Specific examples of nitro oxime compounds include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent Application No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

[0065] Oxime compounds having a benzofuran skeleton can also be used as photopolymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0066] Oxime compounds with hydroxyl substituents bonded to the carbazole backbone can also be used as photopolymerization initiators. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055.

[0067] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group ArOX1 with an electron-withdrawing group introduced into the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic ArOX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano. Acetyl and nitro are preferred, and acetyl is more preferred from the perspective of easily forming a film with excellent lightfastness, while benzoyl is further preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acetyl, or amino groups are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio, or amino groups are even more preferred, and alkoxy, alkylthio, or amino groups are even more preferred.

[0068] The oxime compound OX is preferably selected from at least one of the compounds represented by the free formula (OX1) and the compounds represented by the formula (OX2), with the compound represented by the formula (OX2) being more preferred. [Chemical Formula 4] In the formula, RX1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphinyl, aminomethyl, or aminosulfonyl; RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino; RX3 to RX14 each independently represent a hydrogen atom or a substituent; wherein at least one of RX10 to RX14 is an electron-withdrawing group.

[0069] As electron-withdrawing groups, examples include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl, and cyano. Acetyl and nitro are preferred. Considering the ease with which a film with excellent lightfastness can be formed, acetyl is even more preferred, and benzoyl is even more preferred.

[0070] In the above formula, RX12 is an electron-withdrawing group, and RX10, RX11, RX13 and RX14 are hydrogen atoms, which are preferred.

[0071] As a specific example of an oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 can be cited.

[0072] The following are specific examples of oxime compounds that are preferred for use in the present invention, but the present invention is not limited to these.

[0073]

Chemical Formula 5

Chemical Formula 6

[0074] Oxidime compounds are preferably those with a maximum absorption wavelength in the range of 350–500 nm, and even more preferably those with a maximum absorption wavelength in the range of 360–480 nm. Furthermore, from the viewpoint of sensitivity, it is preferable for the oxime compound to have a high molar absorptivity at wavelengths of 365 nm or 405 nm, more preferably 1,000–300,000, further preferably 2,000–300,000, and particularly preferably 5,000–200,000. The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L with ethyl acetate solvent.

[0075] As a photopolymerization initiator, a photoradical polymerization initiator with two or more functionalities can be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, thus obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, the crystallinity decreases while the solubility in solvents increases, making it difficult to precipitate over time, thereby improving the long-term stability of the photosensitive component. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds described in Japanese Patent Application Publication No. 2013-522445. E) and compounds (G), Cmpd1 to 7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669, etc.

[0076] The content of the photopolymerization initiator in the total solids content of the photosensitive composition is preferably 1 to 10% by mass. The lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less. The photopolymerization initiator can be a single type, or two or more types can be used simultaneously. When two or more types are used simultaneously, it is preferable that their total content is within the above range.

[0077] <<Polymerizable Monomer>> The photosensitive composition of the present invention contains a polymerizable monomer C (hereinafter referred to as the polymerizable monomer) having a group containing an ethylene unsaturated bond. Examples of groups containing an ethylene unsaturated bond in the polymerizable monomer include vinyl, (methyl)allyl, and (meth)acrylyl. The polymerizable monomer system free radical polymerizable monomer used in the present invention is preferred.

[0078] It is preferable that the molecular weight of the polymerizable monomer is 100 or more and less than 3000. It is even more preferable that the upper limit is less than 2000, and even more preferable that it is less than 1500. It is even more preferable that the lower limit is 150 or more, and even more preferable that it is 250 or more. It is also preferable that the polymerizable monomer does not have a molecular weight distribution.

[0079] It is preferable that the polymerizable monomer includes a 1-10 functional polymerizable monomer containing 1 to 10 groups with vinyl unsaturated bonds, more preferably a 2-8 functional polymerizable monomer containing 2 to 8 groups with vinyl unsaturated bonds, and even more preferably a 2-6 functional polymerizable monomer containing 2 to 6 groups with vinyl unsaturated bonds. Furthermore, it is preferable that the polymerizable monomer includes a 1-10 functional (meth)acrylate compound, more preferably a 2-8 functional (meth)acrylate compound, and even more preferably a 2-6 functional (meth)acrylate compound. Specific examples of polymerizable monomers include compounds described in Japanese Patent Application Publication No. 2009-288705 (paragraphs 0095-0108), Japanese Patent Application Publication No. 2013-029760 (paragraph 0227), Japanese Patent Application Publication No. 2008-292970 (paragraphs 0254-0257), Japanese Patent Application Publication No. 2013-253224 (paragraphs 0034-0038), Japanese Patent Application Publication No. 2012-208494 (paragraph 0477), Japanese Patent Application Publication No. 2017-048367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807, the contents of which are incorporated herein by reference.

[0080] The base value (hereinafter also referred to as C=C value) of the polymerizable monomer containing ethylene unsaturated bonds is preferably 1.0 to 15.0 mmol / g. The lower limit is preferably 1.5 mmol / g or higher, and more preferably 2.0 mmol / g or higher. The upper limit is preferably 14.0 mmol / g or lower, and more preferably 12.0 mmol / g or lower.

[0081] As polymerizable monomers, dinepentylenetetroxide triacrylate (commercially available, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dinepentylenetetroxide tetraacrylate (commercially available, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dinepentylenetetroxide penta(meth)acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dinepentylenetetroxide hexa(meth)acrylate (commercially available, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds of the structure in which the (meth)acrylic acid group is linked via ethylene glycol and / or propylene glycol residues (e.g., by SARTOMER) Company, Inc.'s commercially available SR454 and SR499 are preferred. Furthermore, as polymerizable monomers, diglyceride EO (ethylene oxide) modified (meth)acrylate (commercially available, M-460; manufactured by TOAGOSEI CO.,LTD), neopentyl terephthalate tetraacrylate (manufactured by Shin-Nakamura Chemical Co.,Ltd, NK ESTER A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co.,Ltd, KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co.,Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO.,LTD.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co.,Ltd.), and DPHA-40H (manufactured by Nippon Kayaku) are also acceptable. (manufactured by 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 (manufactured by Taisei Fine Chemical Co.,Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co.,LTD.), etc.

[0082] Furthermore, the polymerizable monomer can also be trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, neopentyl tertrol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include ARONIX 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 Co.,Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co.,Ltd.), etc.

[0083] Furthermore, polymerizable monomers can also be compounds containing acid groups. By using polymerizable monomers containing acid groups, it is easier to remove unexposed portions during development, thus suppressing the formation of development residues. Examples of acid groups include carboxyl, sulfonyl, and phosphate groups, with carboxyl being preferred. Examples of polymerizable monomers containing acid groups include succinic acid-modified dinepentylenetetrol pentamethacrylate. Commercially available examples of polymerizable monomers containing acid groups include ARONIX M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO.,LTD.). The preferred acid value for polymerizable monomers containing acid groups is 0.1 to 40 mg KOH / g, more preferably 5 to 30 mg KOH / g. If the acid value of the polymerizable monomer is 0.1 mg KOH / g or higher, its solubility in the developer is good; if it is 40 mg KOH / g or lower, it is advantageous for manufacturing or handling.

[0084] Furthermore, polymerizable monomers having alkoxy groups can also be used. Among polymerizable monomer systems having alkoxy groups, those having ethoxy and / or propoxy groups are preferred, those having ethoxy groups are even more preferred, and 3- to 6-functional (meth)acrylate compounds having 4 to 20 ethoxy groups are further preferred. Commercially available examples of polymerizable monomers having alkoxy groups include, for example, SR-494, a tetrafunctional (meth)acrylate having 4 ethoxy groups, and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutoxy groups, manufactured by SARTOMER Company, Inc.

[0085] It is preferable to use a polymerizable monomer with a basal framework. By using a polymerizable monomer with a basal framework, adsorption with organic pigments can improve the curing degree based on exposure, thereby more significantly achieving the effects of the present invention. A polymerizable monomer with a basal framework and difunctionality is preferred.

[0086] Examples of polymerizable monomers having a basalt skeleton include compounds having a partial structure represented by the following formula (Fr). [Chemical Formula 7]

[0087] In the formula, the wavy line represents the bond, Rf1 and Rf2 independently represent substituents, and m and n independently represent integers from 0 to 5. When m is 2 or more, the m Rf1s can be the same or different, and two Rf1s among the m Rf1s can bond together to form a loop. When n is 2 or more, the n Rf2s can be the same or different, and two Rf2s among the n Rf2s can bond together to form a loop. Examples of substituents represented by Rf1 and Rf2 include halogen atoms, cyano groups, nitro groups, alkyl groups, aryl groups, heteroaryl groups, -ORf11, -CORf12, -COORf13, -OCORf14, -NRf15Rf16, -NHCORf17, -CONRf18Rf19, -NHCONRf20Rf21, -NHCOORf22, -SRf23, -SO2Rf24, -SO2ORf25, -NHSO2Rf26, or -SO2NRf27Rf28. Rf11 to Rf28 independently represent hydrogen atoms, alkyl groups, aryl groups, or heteroaryl groups, respectively.

[0088] Specific examples of polymerizable monomers having a fusiform skeleton include compounds with the following structures. Furthermore, commercially available polymerizable monomers having a fusiform skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fusiform skeleton), etc. [Chemical Formula 8]

[0089] Polymerizable monomers can also be compounds represented by the following formulas (MO-1) to (MO-6). In addition, when T is an oxoalkyl group, the end of the carbon atom is bonded to R.

[0090]

Chemical Formula 9

[0091] In the above formulas, n refers to 0 to 14, and m refers to 1 to 8. A plurality of R and T may be the same or different within a molecule. In each compound represented by the above formulas (MO-1) to (MO-6), at least one of the plurality of R represents -OC(=O)CH=CH2, -OC(=O)C(CH3)=CH2, -NHC(=O)CH=CH2, or -NHC(=O)C(CH3)=CH2. Specific examples of polymerizable compounds represented by the above formulas (MO-1) to (MO-6) include the compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Publication No. 2007-269779.

[0092] It is also preferable to use a compound having a caprolactone structure as the polymerizable monomer. The compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

[0093]

Chemical Formula 10

[0094] In formula (Z-1), all 6 Rs are groups represented by formula (Z-2), or 1 to 5 of the 6 Rs are groups represented by formula (Z-2) and the rest are groups, acid groups or hydroxyl groups represented by formula (Z-3).

[0095]

Chemical Formula 11

[0096]

Chemical Formula 12

[0097] Commercially available products that are polymerizable monomers having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.).

[0098] As a polymerizable monomer, compounds represented by formula (Z-4) or (Z-5) can also be used.

[0099]

Chemical Formula 13

[0100] In formulas (Z-4) and (Z-5), E independently represents -((CH2)yCH2O)- or -((CH2)yCH(CH3)O)-, y independently represents an integer from 0 to 10, and X independently represents a (meth)acrylic acid group, a hydrogen atom, or a carboxyl group. In formula (Z-4), the total number of (meth)acrylic acid groups is 3 or 4, m independently represents an integer from 0 to 10, and the total number of m groups is an integer from 0 to 40. In formula (Z-5), the total number of (meth)acrylic acid groups is 5 or 6, n independently represents an integer from 0 to 10, and the total number of n groups is an integer from 0 to 60.

[0101] In formula (Z-4), it is preferable that m is an integer from 0 to 6, and even more preferable that it is an integer from 0 to 4. Furthermore, it is preferable that the sum of all m is an integer from 2 to 40, even more preferable that it is an integer from 2 to 16, and particularly preferable that it is an integer from 4 to 8. In formula (Z-5), it is preferable that n is an integer from 0 to 6, and even more preferable that it is an integer from 0 to 4. Furthermore, it is preferable that the sum of all n is an integer from 3 to 60, even more preferable that it is an integer from 3 to 24, and particularly preferable that it is an integer from 6 to 12. Furthermore, it is preferable that the terminal bond of the oxygen atom on the X side in formula (Z-4) or formula (Z-5) is attached to X.

[0102] The content of polymerizable monomers in the total solids of the photosensitive composition is preferably 4% by mass or more, and 4 to 20% by mass. The upper limit is preferably 17% by mass or less, and 15% by mass or less is even more preferred. The lower limit is preferably 5% by mass or more, 68% by mass or more is even more preferred, 10% by mass or more is further preferred, and 12% by mass or more is even more preferred.

[0103] Furthermore, relative to 100 parts by weight of the polymeric resin, the content of the polymeric monomer is 5 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 15 to 90 parts by weight, further preferably 20 to 80 parts by weight, and especially preferably 25 to 75 parts by weight.

[0104] Furthermore, the content of polymerizable monomers is preferably 100 to 1000 parts by mass relative to 100 parts by mass of photopolymerization initiator, more preferably 200 to 800 parts by mass, and even more preferably 300 to 600 parts by mass.

[0105] The photosensitive composition of the present invention may contain two or more polymerizable monomers. When the photosensitive composition of the present invention contains two or more polymerizable monomers, the total amount of these monomers is within the above-mentioned range.

[0106] When the photosensitive composition of the present invention comprises two or more polymerizable monomers, it is preferable to use polymerizable monomers with different numbers of groups containing ethylene unsaturated bonds. In this case, it is preferable to use a 1-3 functional polymerizable monomer C1 containing 1-3 ethylene unsaturated bonds and a 4-10 functional polymerizable monomer C2 containing 4-10 ethylene unsaturated bonds. According to this configuration, it is possible to crosslink at a higher density. Furthermore, it is preferable that polymerizable monomer C1 is a difunctional polymerizable monomer. Furthermore, it is preferable that polymerizable monomer C1 is a polymerizable monomer having a basal skeleton. Furthermore, it is preferable that polymerizable monomer C2 is a 4-8 functional polymerizable monomer, and more preferably a 6-8 functional polymerizable monomer. When polymerizable monomer C1 and polymerizable monomer C2 are used simultaneously, regarding the ratio of the two, it is preferable that polymerizable monomer C1 is 10-5000 parts by mass relative to 100 parts by mass of polymerizable monomer C2. The lower limit is 20 parts by mass or more, which is preferred; 30 parts by mass or more, which is even better; 40 parts by mass or more, which is further preferred; and 50 parts by mass or more, which is especially preferred. The upper limit is below 3000 parts by mass, which is preferred; below 2000 parts by mass, which is even better; below 1000 parts by mass, which is further preferred; below 500 parts by mass, which is even more preferred; and below 200 parts by mass, which is especially preferred.

[0107] <<Polymerizable Resin>> The photosensitive composition of the present invention comprises a polymerizable resin D (hereinafter referred to as polymerizable resin) having a group containing an ethylene unsaturated bond. Examples of the ethylene unsaturated bond group in the polymerizable resin include vinyl, (methyl)allyl, (meth)acrylyl, etc.

[0108] It is preferable that the weight average molecular weight of the polymerizable resin is above 3,000, more preferably 3,000 to 50,000, further preferably 5,000 to 50,000, and especially preferably 5,000 to 40,000.

[0109] The C=C value of the polymerizable resin is preferably 0.04 to 2.0 mmol / g. The upper limit is preferably below 1.5 mmol / g, and below 1.0 mmol / g is even better. The lower limit is preferably above 0.1 mmol / g, and above 0.2 mmol / g is even better.

[0110] The polymerizable resin is preferably a resin containing repeating units with side chains having groups containing vinyl unsaturated bonds, and more preferably a resin containing repeating units represented by the following formula (A-1-1). Furthermore, in the polymerizable resin, the content of repeating units having groups containing vinyl unsaturated bonds is preferably 10 mol% or more among all repeating units of the polymerizable resin, more preferably 10 to 80 mol%, and further preferably 20 to 70 mol%. [Chemical Formula 14]

[0111] In formula (A-1-1), X1 represents a trivalent linkage group, L1 represents a single bond or a divalent linkage group, and Y1 represents a group containing an ethylene unsaturated bond.

[0112] As the trivalent linker represented by X1 in formula (A-1-1), examples include poly(meth)acrylic acid linker, polyalkylimide linker, polyester linker, polyurethane linker, polyurea linker, polyamide linker, polyether linker, and polystyrene linker, etc., with poly(meth)acrylic acid linker, polyalkylimide linker and polyester linker being preferred, and poly(meth)acrylic acid linker being even more preferred.

[0113] The divalent linker represented by L1 in formula (A-1-1) can be an alkyl group (preferably an alkyl group having 1 to 12 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), an oxoalkylcarbonyl group (preferably an oxoalkylcarbonyl group having 1 to 12 carbon atoms), an aryl group (preferably an aryl group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these. The alkyl group in the alkyl group, the alkoxy group, and the alkyl group in the oxoalkylcarbonyl group can be any of the following: linear, branched, and cyclic, with linear or branched being preferred. Furthermore, the alkyl group in the alkyl group, the alkoxy group, and the oxoalkylcarbonyl group can have substituents or can be unsubstituted. Examples of substituents include hydroxyl and alkoxy groups. From the viewpoint of manufacturing suitability, hydroxyl is preferred.

[0114] The group containing an ethylene unsaturated bond represented by Y1 in formula (A-1-1) can be vinyl, (meth)allyl, (meth)acrylyl, or styryl, with (meth)acrylyl or styryl being preferred, (meth)acrylyl being even more preferred, and acrylylyl being particularly preferred.

[0115] Specific examples of repeating units represented by formula (A-1-1) include repeating units represented by formula (A-1-1a) and repeating units represented by formula (A-1-1b). [Chemical Formula 15]

[0116] In formula (A-1-1a), Ra1 to Ra3 independently represent hydrogen atoms or alkyl groups, Q1a represents -CO-, -COO-, -OCO-, -CONH-, or a phenyl group, L1 represents a single bond or a divalent linked group, and Y1 represents a group containing an ethylene unsaturated bond. It is preferred that the alkyl groups represented by Ra1 to Ra3 have 1 to 10 carbon atoms, more preferably 1 to 3, and 1 is further preferred. It is preferred that Q1a is -COO- or -CONH-, with -COO- being more preferred.

[0117] In formula (A-1-1b), Ra10 and Ra11 independently represent hydrogen atoms or alkyl groups, m1 represents an integer from 1 to 5, L1 represents a single bond or a divalent linked group, and Y1 represents a group containing an ethylene unsaturated bond. It is preferred that the alkyl groups represented by Ra10 and Ra11 have 1 to 10 carbon atoms, and even more preferred that they have 1 to 3 carbon atoms.

[0118] A polymerizable resin having grafted chains is also preferred. Examples of a resin having grafted chains include resins comprising repeating units having grafted chains. A polymerizable resin having grafted chains can be preferably used as a dispersant. When a polymerizable resin having grafted chains is used, during exposure, the polymerizable resin polymerizes near the colorant, which can firmly retain the colorant in the film and effectively suppress thermal diffusion of these compounds caused by heating. Furthermore, a grafted chain refers to a molecular chain branching from the main chain. Also, the main chain refers to the molecular chain with the most branching points.

[0119] The weight average molecular weight of the grafted chain is preferably 500 to 30,000, more preferably 1,000 to 20,000, and even more preferably 2,000 to 10,000.

[0120] It is preferable that the grafted chain contains a repeating unit selected from the group consisting of at least one structure including polyester, polyether, poly(meth)acrylic acid, polystyrene, polyurethane, polyurea, and polyamide structures; it is even more preferable that it contains a repeating unit selected from the group consisting of polyester, polyether, and poly(meth)acrylic acid structures; and it is further preferable that it contains a repeating unit of polyester structure. Examples of repeating units of polyester structure include repeating units represented by formulas (G-1), (G-4), or (G-5) below. Examples of repeating units of polyether structure include repeating units represented by formula (G-2) below. Examples of repeating units of poly(meth)acrylic acid structure include repeating units represented by formula (G-3) below. [Chemical Formula 16]

[0121] In the above formula, RG1 and RG2 respectively represent alkyl groups. As alkyl groups represented by RG1 and RG2, straight-chain or branched alkyl groups having 1 to 20 carbon atoms are preferred, straight-chain or branched alkyl groups having 2 to 16 carbon atoms are more preferred, and straight-chain or branched alkyl groups having 3 to 12 carbon atoms are even more preferred. In the above formula, RG3 represents a hydrogen atom or a methyl group. In the above formula, QG1 represents -O- or -NH-. In the above formula, LG1 represents a single bond or a divalent linked group. Examples of divalent linkers include alkyl groups (preferably alkyl groups with 1 to 12 carbon atoms), alkoxy groups (preferably alkoxy groups with 1 to 12 carbon atoms), oxoalkylcarbonyl groups (preferably oxoalkylcarbonyl groups with 1 to 12 carbon atoms), aryl groups (preferably aryl groups with 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these. RG4 represents a hydrogen atom or a substituent. Examples of substituents include alkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkyl thioether, aryl thioether, heteroaryl thioether, groups containing vinyl unsaturated bonds, cyclic ether groups, and block isocyanate groups. Examples of groups containing vinyl unsaturated bonds include vinyl, (methyl)allyl, and (methyl)acrylyl. Examples of cyclic ether groups include epoxy group and oxocyclobutyl group.

[0122] The terminal structure of the grafted chain is not particularly limited. It can be a hydrogen atom or a substituent. Examples of substituents include alkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkyl thioether, aryl thioether, and heteroaryl thioether. Among these, from the viewpoint of improving pigment dispersibility, groups with stereorepulsive effects are preferred, and alkyl or alkoxy groups with 5 to 30 carbon atoms are preferred. Alkyl and alkoxy groups can be linear, branched, or cyclic, with linear or branched groups being preferred.

[0123] A polymerizable resin comprising repeating units represented by the following formula (A-1-2) is preferred. [Chemical Formula 17]

[0124] In formula (A-1-2), X2 represents a trivalent linker, L2 represents a single bond or a divalent linker, and W1 represents a graft chain.

[0125] As the trivalent linker represented by X2 in formula (A-1-2), examples include the trivalent linker represented by X1 in formula (A-1-1), and the preferred range is also the same. As the divalent linker represented by L2 in (A-1-2), examples include alkyl groups (preferably alkyl groups having 1 to 12 carbon atoms), aryl groups (preferably aryl groups having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these. As the grafted chain represented by W1 in formula (A-1-2), examples include the above-mentioned grafted chains.

[0126] Specific examples of repeating units represented by formula (A-1-2) include repeating units represented by formula (A-1-2a) and repeating units represented by formula (A-1-2b). [Chemical Formula 18]

[0127] In formula (A-1-2a), Rb1 to Rb3 independently represent hydrogen atoms or alkyl groups, Qb1 represents -CO-, -COO-, -OCO-, -CONH-, or a phenyl group, L2 represents a single bond or a divalent linkage, and W1 represents a grafted chain. It is preferred that the alkyl group represented by Rb1 to Rb3 has 1 to 10 carbon atoms, more preferably 1 to 3, and 1 is further preferred. It is preferred that Qb1 is -COO- or -CONH-, and more preferably -COO-.

[0128] In formula (A-1-2b), Rb10 and Rb11 independently represent hydrogen atoms or alkyl groups, m2 represents an integer from 1 to 5, L2 represents a single bond or a divalent linkage, and W1 represents a grafted chain. It is preferred that the carbon number of the alkyl group represented by Rb10 and Rb11 is 1 to 10, and even more preferred that it is 1 to 3.

[0129] When the polymerizable resin contains repeating units with grafted chains, it is preferable that the weight-average molecular weight (Mw) of the repeating units with grafted chains is 1000 or more, more preferably 1000 to 10000, and even more preferably 1000 to 7500. Furthermore, in this invention, the weight-average molecular weight of the repeating units with grafted chains is a value calculated from the weight-average molecular weight of the raw material monomers used in the polymerization of the same repeating unit. For example, repeating units with grafted chains can be formed by polymerizing macromonomers. Here, a macromonomer refers to a polymer compound with a polymerizable group introduced at the polymer terminus. When using macromonomers to form repeating units with grafted chains, the weight-average molecular weight of the macromonomer corresponds to the repeating unit with grafted chains.

[0130] When the polymeric resin contains repeating units represented by formula (A-1-2), the content of repeating units represented by formula (A-1-2) is preferably 1.0 to 60 mol% among all repeating units of the polymeric resin, and more preferably 1.5 to 50 mol%.

[0131] It is also preferable that the polymerizable resin further includes repeating units having acid groups. By further including repeating units having acid groups in the polymerizable resin, the dispersibility of pigments, etc., can be further improved. Furthermore, the developability can also be improved. Examples of acid groups include carboxyl groups, sulfonyl groups, and phosphate groups.

[0132] When the polymeric resin contains repeating units having acid groups, it is preferable that the content of repeating units having acid groups is 80 mol% or less, and more preferably 10 to 80 mol% among all repeating units of the polymeric resin. When the polymeric resin contains repeating units having acid groups, it is preferable that the acid value of the polymeric resin is 20 to 150 mg KOH / g. The upper limit is preferably 100 mg KOH / g or less. The lower limit is preferably 30 mg KOH / g or more, and more preferably 35 mg KOH / g or more. As long as the acid value of the polymeric resin is within the above range, it is particularly easy to obtain excellent dispersibility. Furthermore, it is easy to obtain excellent developability.

[0133] A polymeric resin containing a repeating unit represented by formula (Ac-1) is also preferred.

Chemical Formula 19

[0134] In formula (Ac-1), the aromatic carboxyl group represented by Ar10 can be represented by structures derived from aromatic tricarboxylic anhydrides, aromatic tetracarboxylic anhydrides, etc. Compounds with the following structures can be cited as aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides. [Chemical Formula 20]

[0135] In the above formula, Q1 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 21

Chemical Formula 22

[0136] In formula (Ar-11), n1 represents an integer from 1 to 4, preferably 1 or 2, and more preferably 2. In formula (Ar-12), n2 represents an integer from 1 to 8, preferably an integer from 1 to 4, more preferably 1 or 2, and more preferably 2. In formula (Ar-13), n3 and n4 each independently represent an integer from 0 to 4, preferably an integer from 0 to 2, more preferably 1 or 2, and more preferably 1. At least one of n3 and n4 is an integer greater than or equal to 1. In formula (Ar-13), Q1 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 formulas (Ar-11) to (Ar-13), *1 indicates the bond position with L11.

[0137] In formula (Ac-1), L11 represents -COO- or -CONH-, with -COO- being preferred.

[0138] The trivalent linker represented by L12 in formula (Ac-1) can be a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, or a combination of two or more of these. Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Aliphatic hydrocarbon groups are preferably composed of 1 to 30 carbon atoms, more preferably 1 to 20, and further preferably 1 to 15. Aliphatic hydrocarbon groups can be straight-chain, branched, or cyclic. Aromatic hydrocarbon groups are preferably composed of 6 to 30 carbon atoms, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group can have substituents. Examples of substituents include hydroxyl groups. The trivalent linker represented by L12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).

Chemical Formula 23

[0139] In formula (L12-1), L12b represents a trivalent linker, X1 represents S, *1 represents the bond position with L11 in formula (Ac-1), and *2 represents the bond position with P10 in formula (Ac-1). Examples of the trivalent linker represented by L12b include hydrocarbon groups; preferably, the hydrocarbon group or a group formed by combining a hydrocarbon group with at least one of -O-, -CO-, -COO-, -OCO-, -NH-, and -S- is a hydrocarbon group or a group formed by combining a hydrocarbon group with -O-.

[0140] In formula (L12-2), L12c represents a trivalent linker, X1 represents S, *1 represents the bond position with L11 in formula (Ac-1), and *2 represents the bond position with P10 in formula (Ac-1). Examples of trivalent linkers represented by L12c include hydrocarbon groups; a hydrocarbon group is preferred as a combination of the hydrocarbon group and at least one group selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-.

[0141] P10 in formula (Ac-1) represents a polymer chain having a group containing an ethylene unsaturated bond. It is preferable that the polymer chain represented by P10 includes a repeating unit selected from the group consisting of at least one structure including polyester, polyether, poly(meth)acrylic acid, polystyrene, polyurethane, polyurea, and polyamide structures; more preferably, it includes a repeating unit selected from the group consisting of polyester, polyether, and poly(meth)acrylic acid structures; and even more preferably, it includes a repeating unit of polyester structure. Examples of repeating units of polyester structure include those represented by formulas (G-1), (G-4), or (G-5) above. Examples of repeating units of polyether structure include those represented by formula (G-2) above. Examples of repeating units of poly(meth)acrylic acid structure include those represented by formula (G-3) above.

[0142] Furthermore, regarding the polymer chain represented by P10, it is preferable that the proportion of repeating units containing groups with ethylene unsaturated bonds in the side chains among all repeating units constituting P10 is 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit can be set to 100% by mass, preferably 90% by mass or less, and even more preferably 60% by mass or less.

[0143] Furthermore, it is preferable that the polymer chain represented by P10 has repeating units containing acid groups. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups. According to this configuration, the dispersibility of the pigment in the composition can be further improved. Furthermore, the developability can also be further improved. The proportion of repeating units containing acid groups is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass.

[0144] The weight average molecular weight of the polymer chain represented by P10 is preferably 500 to 20,000. A lower limit of 600 or more is preferred, and 1,000 or more is even more preferred. An upper limit of 10,000 or less is preferred, 5,000 or less is even more preferred, and 3,000 or less is even more preferred. As long as the weight average molecular weight of P10 is within the above range, the pigment has good dispersibility in the composition. This resin can be preferably used as a dispersant.

[0145] The weight-average molecular weight of the resin containing repeating units represented by formula (Ac-1) is preferably 3,000 to 35,000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and further preferably 15,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more, and further preferably 6,000 or more.

[0146] The acid value of the resin containing repeating units represented by formula (Ac-1) is preferably 5 to 200 mg KOH / g. The upper limit is preferably 150 mg KOH / g or less, more preferably 100 mg KOH / g or less, and further preferably 80 mg KOH / g or less. The lower limit is preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, and further preferably 20 mg KOH / g or more.

[0147] The content of polymeric resin in the total solids of the photosensitive composition is preferably 1 to 40% by mass. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and especially preferably 18% by mass or more. Furthermore, the total mass of polymeric monomers and polymeric resin in the total solids of the photosensitive composition is preferably 5 to 45% by mass. The upper limit is preferably 40% by mass or less, and more preferably 38% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

[0148] The photosensitive composition of the present invention may contain two or more polymeric resins. When the photosensitive composition of the present invention contains two or more polymeric resins, the total amount of these resins is within the above-mentioned range.

[0149] <<Other Resins>> The photosensitive composition of the present invention may contain resins other than the polymerizable resins described above (hereinafter also referred to as other resins). For example, other resins may be incorporated for purposes such as dispersing pigments in the photosensitive composition or as adhesives. In addition, resins primarily used for dispersing pigments are also referred to as dispersants. However, such uses of resins are only one example; they may also be used for purposes other than such uses.

[0150] The weight average molecular weight (Mw) of other resins is preferably between 3,000 and 2,000,000. The upper limit is preferably below 1,000,000, and below 500,000 is even more preferred. The lower limit is preferably above 4,000, and above 5,000 is even more preferred.

[0151] Examples of other resins include (meth)acrylic resin, olefin-thiol resin, polycarbonate resin, polyether resin, polyaryl ester resin, polyurethane resin, polyetherurethane resin, polystyrene resin, polyaryl ether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, and styrene resin. Of these resins, one may be used alone, or two or more may be used in combination. Furthermore, the resins described in paragraphs 0041 to 0060 of Japanese Patent Application Publication No. 2017-206689, the resins described in paragraphs 0022 to 0071 of Japanese Patent Application Publication No. 2018-010856, the resins described in Japanese Patent Application Publication No. 2017-057265, the resins described in Japanese Patent Application Publication No. 2017-032685, the resins described in Japanese Patent Application Publication No. 2017-075248, and the resins described in Japanese Patent Application Publication No. 2017-066240 can also be used.

[0152] As other resins, resins having acid groups are preferred. According to this, the developability of the pixel-forming composition can be improved. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups, with carboxyl groups being preferred. For example, resins having acid groups can be used as alkali-soluble resins. It is preferable that the resin having acid groups comprises repeating units with acid groups in the side chains, and it is even more preferable that the resin comprises 5 to 70 mol% of repeating units with acid groups in the side chains in all repeating units of the resin. It is further preferable that the upper limit of the content of repeating units with acid groups in the side chains is 50 mol% or less, and particularly preferable that it is 30 mol% or less. It is further preferable that the lower limit of the content of repeating units with acid groups in the side chains is 10 mol% or more, and particularly preferable that it is 20 mol% or more. Regarding resins containing acid groups, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of U.S. Patent Application Publication No. 2012 / 0235099) and paragraphs 0076 to 0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference. Furthermore, commercially available resins containing acid groups may also be used.

[0153] Other resins can also be used as dispersants. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups exceeds the amount of base groups. Regarding acidic dispersants (acidic resins), when the total amount of acid groups and base groups is set to 100 mol%, a resin in which the amount of acid groups accounts for 70 mol% or more is preferred, and a resin substantially composed only of acid groups is even more preferred. It is preferable that the acid groups in the acidic dispersant (acidic resin) are carboxyl groups. It is preferable that the acid value of the acidic dispersant (acidic resin) is 40–105 mg KOH / g, more preferably 50–105 mg KOH / g, and further preferably 60–105 mg KOH / g. Furthermore, basic dispersant (basic resin) refers to a resin in which the amount of base groups exceeds the amount of acid groups. Regarding alkaline dispersants (alkaline resins), when the total amount of acid groups and base groups is set to 100 mol%, resins with a base group amount exceeding 50 mol% are preferred. It is preferable that the base group in the alkaline dispersant is an amine group. Furthermore, it is also preferable that the resin used as a dispersant is a grafted resin. As a grafted resin, the resin described in paragraphs 0025 to 0094 of Japanese Patent Application Publication No. 2012-255128 can be cited as an example, the contents of which are incorporated in this specification. Furthermore, it is also preferable that the resin used as a dispersant is a polyimide-based dispersant containing a nitrogen atom in at least one of the main chain and side chains. As a polyimide-based dispersant, it is preferable that the resin has a main chain and side chains, and that at least one of the main chain and side chains has an alkaline nitrogen atom, wherein the main chain contains a partial structure with a functional group having a pKa of 14 or less, and the side chains have 40 to 10,000 atoms. There are no particular restrictions as long as the basic nitrogen atom is a basic nitrogen atom. As a polyimide-based dispersant, the resin described in paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, the contents of which are incorporated herein by reference. Furthermore, resins used as dispersants with a structure in which multiple polymer chains are bonded to the core are also preferred. Examples of such resins include dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymers C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962. Furthermore, dispersants may also include polyethyleneimine with polyester side chains as described in International Patent Publication No. 2016 / 104803, block copolymers as described in International Patent Publication No. 2019 / 125940, block polymers with acrylamide structural units as described in Japanese Patent Application Publication No. 2020-066687, and block polymers with acrylamide structural units as described in Japanese Patent Application Publication No. 2020-066688.Furthermore, dispersants are also available as commercially available products. Specific examples include the DISPERBYK series (e.g., DISPERBYK-111, 161, etc.) manufactured by BYK-Chemie GmbH and the SOLSPERSE series (e.g., SOLSPERSE 76500, etc.) manufactured by Lubrizol Japan Ltd. Additionally, pigment dispersants described in paragraphs 0041 to 0130 of Japanese Patent Application Publication No. 2014-130338 can also be used, as this specification is incorporated herein by reference. Furthermore, the resins described as dispersants can also be used for purposes other than dispersants. For example, they can also be used as adhesives.

[0154] The content of other resins in the total solids of the photosensitive composition is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and especially preferably 0.5% by mass or less. Furthermore, the total content of the aforementioned polymeric resin and other resins in the total solids of the photosensitive composition is preferably 1 to 40% by mass. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and especially preferably 18% by mass or more. There may be only one type of other resin, or there may be two or more types. When two or more types are included, it is preferable that their total content is within the above-mentioned range.

[0155] <<Pigment Derivatives>> The photosensitive composition of the present invention can contain pigment derivatives. Examples of pigment derivatives include compounds having a structure in which acid groups or base groups are bonded to a pigment skeleton. Examples of pigment skeletons constituting pigment derivatives include quinoline pigment skeletons, benzimidazolone pigment skeletons, benzoindole pigment skeletons, benzothiazole pigment skeletons, iminocyanine pigment skeletons, squaric acid cyanine pigment skeletons, ketoneonium pigment skeletons, oxacyanine pigment skeletons, pyrrolopyrrole pigment skeletons, diketopyrrolopyrrole pigment skeletons, azo pigment skeletons, azomethine pigment skeletons, phthalocyanine pigment skeletons, naphthylphthalocyanine pigment skeletons, anthraquinone pigment skeletons, quinacrine pigment skeletons, dioxane pigment skeletons, violet ketone pigment skeletons, perylene pigment skeletons, thioindole pigment skeletons, isoindoleline pigment skeletons, isoindolelineone pigment skeletons, quinoline yellow pigment skeletons, iminocyanine pigment skeletons, dithiol pigment skeletons, triarylmethane pigment skeletons, and pyrrole methylene pigment skeletons. Examples of acid groups include sulfonyl, carboxyl, and phosphate groups, and their salts. Examples of atoms or groups constituting salts include alkali metal ions (Li+, Na+, K+, etc.), alkaline earth metal ions (Ca2+, Mg2+, etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc. Examples of base groups include amino, pyridinium and their salts, ammonium salts, and phthalimide methyl groups. Examples of atoms or groups constituting salts include hydroxide ions, halide ions, carboxylic acid ions, sulfonic acid ions, phenoxy ions, etc.

[0156] Pigment derivatives with excellent visible transparency (hereinafter also referred to as transparent pigment derivatives) can also be used. The maximum value (εmax) of the molar absorptivity of the transparent pigment derivative in the wavelength region of 400–700 nm is preferably 3000 L·mol⁻¹·cm⁻¹ or less, more preferably 1000 L·mol⁻¹·cm⁻¹ or less, and even more preferably 100 L·mol⁻¹·cm⁻¹ or less. For example, the lower limit of εmax is 1 L·mol⁻¹·cm⁻¹ or more, and can also be 10 L·mol⁻¹·cm⁻¹ or more.

[0157] Specific examples of pigment derivatives include the compounds described in the following examples, Japanese Patent Application Publication No. 56-118462, Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 01-217077, Japanese Patent Application Publication No. 03-009961, Japanese Patent Application Publication No. 03-026767, Japanese Patent Application Publication No. 03-153780, Japanese Patent Application Publication No. 03-045662, Japanese Patent Application Publication No. 04-285669, Japanese Patent Application Publication No. 06-145546, Japanese Patent Application Publication No. 06-212088, Japanese Patent Application Publication No. 06-240158, Japanese Patent Application Publication No. 10-030063, Japanese Patent Application Publication No. 10-195326, and international publications. Japanese Patent Application Publication No. 2011 / 024896, paragraphs 0086-0098; Japanese Patent Application Publication No. 2012 / 102399, paragraphs 0063-0094; Japanese Patent Application Publication No. 2017 / 038252, paragraph 0082; Japanese Patent Application Publication No. 2015-151530, paragraph 0171; Japanese Patent Application Publication No. 2011-252065, paragraphs 0162-0183; Japanese Patent Application Publication No. 2011-252065, paragraphs 0086-0098; Japanese Patent Application Publication No. 2012 / 102399, paragraphs 0063-0094; Japanese Patent Application Publication No. 2017 / 038252, paragraph 0082; Japanese Patent Application Publication No. 2015-151530, paragraph 0171; Japanese Patent Application Publication No. 2015-151530, paragraphs 0162-0183; Japanese Patent Application Publication No. 2011-252065, paragraphs 0162-0183; Japanese Patent Application Publication No. 2011-252065, paragraphs 0086-0098; Japanese Patent Application Publication No. 2011 / 024896, paragraphs 0086-0098; Japanese Patent Application Publication No. 2012 / 102399, paragraphs 0063-0094; Japanese Patent Application Publication No. 2017 / 038252, paragraph 0082; Japanese Patent Application Publication No. 2017-038252, paragraph 0081; Japanese Patent Application Publication No. 2015-151530 The compounds described in Japanese Patent Application Publication No. 2003-081972, Japanese Patent No. 5299151, Japanese Patent Application Publication No. 2015-172732, Japanese Patent Application Publication No. 2014-199308, Japanese Patent Application Publication No. 2014-085562, Japanese Patent Application Publication No. 2014-035351, and Japanese Patent Application Publication No. 2008-081565.

[0158] The content of pigment derivatives relative to 100 parts by weight of colorant is preferably 1 to 30 parts by weight, and more preferably 3 to 20 parts by weight. One type of pigment derivative can be used alone, or two or more types can be used simultaneously. When two or more types are used simultaneously, the total amount of these derivatives is preferably within the above range.

[0159] <<Polyalkylimine>> The photosensitive composition of the present invention may also contain polyalkylimine. Polyalkylimine is a polymer formed by ring-opening polymerization of alkylimine, and is a polymer having a branched structure comprising primary, secondary, and tertiary amino groups respectively. The carbon number of the alkylimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and especially preferably 2.

[0160] The molecular weight of the polyalkylimide is preferably 200 or higher, and more preferably 250 or higher. The upper limit is preferably 100,000 or lower, more preferably 50,000 or lower, further preferably 10,000 or lower, and especially preferably 2,000 or lower. Furthermore, regarding the molecular weight of the polyalkylimide, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylimide is the value calculated from the structural formula. On the other hand, when the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the number average molecular weight value determined by the boiling point rise method is used. Also, when the molecular weight cannot be determined by the boiling point rise method or is difficult to determine, the number average molecular weight value determined by the viscosity method is used. Furthermore, when the molecular weight cannot be determined by the viscosity method or is difficult to determine by the viscosity method, the number average molecular weight value converted from the polystyrene value determined by GPC (gel permeation chromatography) is used.

[0161] The amine value of polyalkylimide is preferably 5 mmol / g or higher, more preferably 10 mmol / g or higher, and even more preferably 15 mmol / g or higher.

[0162] Specific examples of polyalkylimides include ethyleneimide, propyleneimide, 1,2-buteneimide, and 2,3-buteneimide, with ethyleneimide or propyleneimide being preferred, and ethyleneimide being even more preferred. Polyalkylimide-based polyethyleneimide is particularly preferred. Furthermore, in polyethyleneimide, it is preferable to contain 10 mol% or more of primary amino groups, more preferable to contain 20 mol% or more, and even more preferable to contain 30 mol% or more, relative to the total of primary, secondary, and tertiary amino groups. Commercially available polyethyleneimides include EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by NIPPON SHOKUBAI CO.,LTD.).

[0163] The content of alkylimide in the total solids of the photosensitive composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less. Furthermore, the content of alkylimide relative to 100 parts by mass of pigment is preferably 0.5 to 10 parts by mass. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more. The upper limit is preferably 8 parts by mass or less, more preferably 7% by mass or less, and further preferably 5 parts by mass or less. Only one type of alkylimide may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above-mentioned range.

[0164] <<Compounds with Cyclic Ether Groups>> The photosensitive composition of the present invention can contain compounds with cyclic ether groups. Examples of cyclic ether groups include epoxy groups and oxocyclobutyl groups. It is preferable that the compound with a cyclic ether group is a compound with epoxy groups (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include compounds having one or more epoxy groups per molecule, and compounds having two or more epoxy groups are preferred. It is preferable that the epoxy compound has 1 to 100 epoxy groups per molecule. For example, the upper limit of the number of epoxy groups contained in the epoxy compound can be set to 10 or less, or even 5 or less. It is preferable that the lower limit of the number of epoxy groups contained in the epoxy compound is two or more. As epoxy-based compounds, compounds described in Japanese Patent Application Publication No. 2013-011869 (paragraphs 0034-0036), Japanese Patent Application Publication No. 2014-043556 (paragraphs 0147-0156), Japanese Patent Application Publication No. 2014-089408 (paragraphs 0085-0092), and Japanese Patent Application Publication No. 2017-179172 can also be used. These contents are incorporated herein by reference.

[0165] The epoxy compound can be a low molecular weight compound (e.g., molecular weight less than 2000, and further less than 1000) or a macromolecule (e.g., molecular weight 1000 or more, and in the case of a polymer, a weight average molecular weight 1000 or more). It is preferable that the weight average molecular weight of the compound having epoxy groups is 200 to 100,000, and more preferably 500 to 50,000. It is further preferable that the upper limit of the weight average molecular weight is below 10,000, particularly preferably below 5,000, and even more preferably below 3,000.

[0166] Epoxy resins are preferred as epoxy compounds. Examples of epoxy resins include epoxy resins that are epoxy propylene ethers of phenolic compounds, epoxy resins that are epoxy propylene ethers of various phenolic varnish resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, epoxy propylene ester epoxy resins, epoxy propylene amine epoxy resins, epoxy resins obtained by epoxypropylating halogenated phenols, fused compounds of silicone compounds having epoxy groups and other silicone compounds, and copolymers of polymerizable unsaturated compounds having epoxy groups and other polymerizable unsaturated compounds. The epoxy equivalent of the epoxy resin is preferably 310–3300 g / eq, more preferably 310–1700 g / eq, and even more preferably 310–1000 g / eq.

[0167] Commercially available products containing cyclic ether groups include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC CORPORATION), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all of which are manufactured by NOF CORPORATION and contain epoxy groups).

[0168] The content of the compound having a cyclic ether group in the total solids content of the photosensitive composition is preferably 0.1 to 20% by mass. For example, the lower limit is preferably 0.5% by mass or more, and 1% by mass or more is further preferred. For example, the upper limit is preferably 15% by mass or less, and 10% by mass or less is further preferred. 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-mentioned range.

[0169] <<Curing Accelerator>> The photosensitive composition of the present invention may include a curing accelerator. Examples of curing accelerators include thiol compounds, hydroxymethyl compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, alkane generating agents, isocyanate compounds, alkoxysilane compounds, onium salt compounds, etc. Specific examples of curing accelerators include compounds described in paragraphs 0094 to 0097 of International Publication No. 2018 / 056189, compounds described in paragraphs 0246 to 0253 of Japanese Patent Application Publication No. 2015-034963, compounds described in paragraphs 0186 to 0251 of Japanese Patent Application Publication No. 2013-041165, and compounds described in Japanese Patent Application Publication No. 2014-055114. The compounds described herein include ionic compounds, compounds described in paragraphs 0071 to 0080 of Japanese Patent Application Publication No. 2012-150180, alkoxysilane compounds described in Japanese Patent Application Publication No. 2011-253054, compounds described in paragraphs 0085 to 0092 of Japanese Patent Application Publication No. 5765059, and carboxyl-containing epoxy curing agents described in Japanese Patent Application Publication No. 2017-036379. The curing accelerator is preferably present in a content of 0.3 to 8.9% by mass in the total solids of the photosensitive composition, and more preferably in a content of 0.8 to 6.4% by mass.

[0170] <<Surfactant>> The photosensitive composition of the present invention can contain a surfactant. Various surfactants, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants, can be used as surfactants. Regarding surfactants, those described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779 are cited as examples, the contents of which are incorporated herein by reference.

[0171] Fluorinated surfactants are preferred. By including fluorinated surfactants in the photosensitive composition, the liquid properties (especially flowability) are further improved, and the liquid-saving properties can be further enhanced. In addition, it is also possible to form a film with less uneven thickness.

[0172] The fluorine content in fluorinated surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and especially preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniform coating thickness and liquid saving, and also have good solubility in photosensitive components.

[0173] Examples of fluorinated surfactants include those described in paragraphs 0060-0064 of Japanese Patent Application Publication No. 2014-041318 (corresponding to paragraphs 0060-0064 of International Publication No. 2014 / 017669), those described in paragraphs 0117-0132 of Japanese Patent Application Publication No. 2011-132503, and those described in Japanese Patent Application Publication No. 2020-008634, the contents of which are incorporated herein by reference. Commercially available examples of fluorinated surfactants include, for example, MEGAFACE. 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, 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 (the above are DIC) (manufactured by CORPORATION), FLUORAD FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), 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 PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA SOLUTIONS INC.), Futurgent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218 (all manufactured by NEOS COMPANY LIMITED), etc.

[0174] Furthermore, fluorinated surfactants can also better utilize acrylic compounds, which contain a molecular structure with a functional group containing a fluorine atom, and upon heating, the portion containing the fluorine atom is cleaved and the fluorine atom volatilizes. Examples of such fluorinated surfactants include the MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)), such as MEGAFACE DS-21.

[0175] Furthermore, regarding fluorinated surfactants, polymers of fluorinated vinyl ether compounds having fluorinated alkyl or fluorinated alkyl ether groups and hydrophilic vinyl ether compounds are preferred. Examples of such fluorinated surfactants include those described in Japanese Patent Application Publication No. 2016-216602, the contents of which are incorporated herein by reference.

[0176] Fluorinated surfactants can also be used with block polymers. Fluorinated surfactants can also preferably be used with fluorinated polymers comprising: repeating units from (meth)acrylate compounds having fluorine atoms; and repeating units from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propoxy). Furthermore, the fluorinated surfactants described in paragraphs 0016 to 0037 of Japanese Patent Application Publication No. 2010-032698, and the following compounds are also exemplified as fluorinated surfactants used in this invention. [Chemical Formula 24] The weight average molecular weight of the above compounds is preferably 3000 to 50000, for example, 14000. In the above compounds, the percentage of repeating units is in moles.

[0177] Furthermore, fluorinated surfactants can also be used on fluoropolymers having groups containing vinyl unsaturated bonds on their side chains. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, and MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation. Additionally, fluorinated surfactants can also be used with compounds described in paragraphs 0015-0158 of Japanese Patent Application Publication No. 2015-117327.

[0178] Furthermore, from an environmental control point of view, it is also better to use the surfactant described in International Publication No. 2020 / 084854 as a substitute for surfactants with a carbon number of 6 or more perfluoroalkyl groups.

[0179] Furthermore, it is preferable to use the fluoroimidide salt compound represented by formula (fi-1) as a surfactant.

Chemical Formula 25

[0180] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), and Solsperse 20000 (Japan Lubrizol). (Manufactured by FUJIFILM Wako Pure Chemical Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

[0181] Examples of polysiloxane surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, and KF-6002 (manufactured by Shin-Etsu Chemical). BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie GmbH), FZ-2122 (manufactured by Dow Corning Toray Co., Ltd.), etc.

[0182] Furthermore, compounds with the following structure can also be used in polysiloxane-based surfactants. [Chemical Formula 26]

[0183] The content of surfactant 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. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount within the above range is preferred.

[0184] <<Solvent>> The photosensitive composition of the present invention can contain a solvent. There are essentially no particular limitations on the type of solvent, as long as it satisfies the solubility of each component and the coatability of the composition. Organic solvents are preferred. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details regarding these, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. Furthermore, ester solvents with cyclic alkyl substituted structures and ketone solvents with cyclic alkyl substituted structures are also preferred. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib 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, and ethyl carbitol. Acetates, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, cyclobutane, anisole, 1,4-diethoxybutane, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol, etc. However, sometimes for environmental reasons, it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents (for example, relative to the total amount of organic solvents, it can be set to 50 ppm (parts per million), 10 ppm, or 1 ppm).

[0185] In this invention, it is preferable to use organic solvents with low metal content, for example, the metal content of the organic solvent is preferably below 10 ppb (parts per billion). Organic solvents at the ppt (parts per trillion) level can be used as needed, such organic solvents are provided, for example, by Toyo Gosei Co., Ltd (Chemical Industry Daily, November 13, 2015).

[0186] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, membrane distillation, etc.) or filtration using a filter. The filter pore size is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0187] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). Furthermore, isomers may contain only one type or multiple types.

[0188] It is preferable that the peroxide content in the organic solvent is below 0.8 mmol / L, and it is even better if the solvent does not contain peroxide at all.

[0189] 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. From the viewpoint of coatability, the lower limit is preferably 20% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, even more preferably 75% by mass or more, and even more preferably 80% by mass or more.

[0190] Furthermore, from an environmental control perspective, it is preferable that the photosensitive composition of the present invention is substantially free of environmentally regulated substances. In the present invention, "substantially free of 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, further preferably 10 ppm by mass or less, and especially 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 based on the REACH (Registration Evaluation Authorization and Restriction of Chemicals) Act, the PRTR (Pollutant Release and Transfer Register) Act, and VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly controlled. Regarding these compounds, they are sometimes used as solvents in the manufacture of various components used in the photosensitive composition, and sometimes they are mixed into the photosensitive composition as residual solvents. From the perspectives of human safety and environmental protection, it is preferable to minimize the amount of such substances. One method for reducing environmentally regulated substances is to heat and depressurize the system to a temperature above the boiling point of the substance, thereby removing it from the system through distillation and reducing the amount of environmentally regulated substances. Furthermore, when distilling away small amounts of environmentally regulated substances, it is useful to azeotropically distill them with a solvent having the same boiling point as the original solvent to improve efficiency. Also, when the substance contains compounds with free radical polymerization potential, polymerization inhibitors can be added for vacuum distillation to inhibit free radical polymerization reactions that could lead to intermolecular cross-linking during vacuum distillation. These distillation removal methods can be implemented at any stage, including the raw material stage, the product stage (e.g., polymerized resin solution, multifunctional monomer solution), or the stage of preparing a photosensitive composition by mixing these compounds.

[0191] <<Silane Coupling Agent>> The photosensitive composition of the present invention may contain a silane coupling agent. In this specification, a silane coupling agent refers to a silane compound having a hydrolyzable group and other functional groups. Furthermore, a hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and aceoxy groups, with alkoxy groups being preferred. That is, a silane coupling agent is preferably a compound having an alkoxysilyl group. Furthermore, as functional groups other than hydrolyzable groups, examples include vinyl, (meth)allyl, (meth)acrylyl, mercapto, epoxy, oxetyl, amino, urea, thioether, isocyanate, phenyl, etc., with amino, (meth)acrylyl and epoxy being more preferred. Specific examples of silane coupling agents include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-903), and γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-903). (Manufactured by Shin-Etsu Chemical Co., Ltd., product name KBE-903), 3-methylpropenoxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-502), 3-methylpropenoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-503), etc. Specific examples of silane coupling agents include compounds described in paragraphs 0018 to 0036 of Japanese Patent Application Publication No. 2009-288703 and compounds described in paragraphs 0056 to 0066 of Japanese Patent Application Publication No. 2009-242604, the contents of which are incorporated herein by reference. The content of the silane coupling agent in the total solids of the photosensitive composition is preferably 0.1% to 5% by mass. The upper limit is preferably 3% by mass or less, and 2% by mass or less is further preferred. The lower limit is preferably 0.5% by mass or more, and 1% by mass or more is further preferred. Only one type of silane coupling agent 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-mentioned range.

[0192] <<Ultraviolet Absorber>> The photosensitive composition of the present invention can contain an ultraviolet absorber. The ultraviolet absorber can be a conjugated diene compound, an amino diene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl trioxide compound, an indole compound, a trioxide compound, etc. Examples of such compounds include those described in paragraphs 0038 to 0052 of Japanese Patent Application Publication No. 2009-217221, paragraphs 0052 to 0072 of Japanese Patent Application Publication No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Application Publication No. 2013-068814, and paragraphs 0061 to 0080 of Japanese Patent Application Publication No. 2016-162946, the contents of which are incorporated herein by reference. Commercially available ultraviolet absorbers include, for example, UV-503 (manufactured by DAITO CHEMICAL CO.,LTD.). Also, as benzotriazole compounds, the MYUA series manufactured by MIYOSHI OIL & FAT CO.,LTD. (Chemical Industry Daily, February 1, 2016). Furthermore, compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as ultraviolet absorbers. The content of the ultraviolet absorber in the total solids of the photosensitive component is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber can be used, or two or more types can be used. When using two or more types, the total amount within the above-mentioned range is preferred.

[0193] <<Antioxidant>> The photosensitive composition of the present invention can contain an antioxidant. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be used. Compounds having a substituent at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the aforementioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenolic group and a phosphite group in the same molecule are also preferred as antioxidants. Furthermore, phosphorus-based antioxidants are also preferred as antioxidants. Furthermore, compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used as antioxidants. The content of the antioxidant in the total solids content of the photosensitive composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. One type of antioxidant may be used, or two or more may be used. When using two or more, it is preferable to keep the total dosage within the range mentioned above.

[0194] <<Polymerization Inhibitor>> The photosensitive composition of the present invention can contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di- and tri-butyl-p-cresol, gallnutol, tri-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tri-butylphenol), 2,2'-methylenebis(4-methyl-6-tri-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, cerium salts, etc.). Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solids of the photosensitive composition is preferably 0.0001 to 5% by mass. There may be only one type of polymerization inhibitor, or there may be two or more types. In the case of two or more types, the total amount is preferably within the above range.

[0195] <<Other Ingredients>> In this invention, the photosensitive composition may contain, as needed, sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other additives (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately containing these ingredients, the physical properties of the film can be adjusted. Regarding these ingredients, for example, reference can be made to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. Furthermore, the photosensitive composition of this invention may contain potential antioxidants as needed. Compounds that can be cited as potential antioxidants include those whose sites of antioxidant activity are protected by a protecting group, and which function as antioxidants by being deactivated by heating at 100–250°C or heating at 80–200°C in the presence of an acid / base catalyst. Compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 are examples of potential antioxidants. Commercially available products that can be cited as potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

[0196] The photosensitive composition of the present invention may include a lightfastness modifier. Examples of lightfastness modifiers include compounds described in paragraphs 0036-0037 of Japanese Patent Application Publication No. 2017-198787, compounds described in paragraphs 0029-0034 of Japanese Patent Application Publication No. 2017-146350, compounds described in paragraphs 0036-0037 and 0049-0052 of Japanese Patent Application Publication No. 2017-129774, and compounds described in Japanese Patent Application Publication No. 201... The compounds described in paragraphs 0031-0034 and 0058-0059 of Japanese Patent Application Publication No. 7-129674, the compounds described in paragraphs 0036-0037 and 0051-0054 of Japanese Patent Application Publication No. 2017-122803, the compounds described in paragraphs 0025-0039 of International Patent Application Publication No. 2017 / 164127, and the compounds described in Japanese Patent Application Publication No. 2017-186546 The compounds described in paragraphs 0034 to 0047 of the Japanese Patent Application Publication No. 2015-025116, the compounds described in paragraphs 0019 to 0041 of the Japanese Patent Application Publication No. 2012-145604, the compounds described in paragraphs 0101 to 0125 of the Japanese Patent Application Publication No. 2012-103475, the compounds described in paragraphs 0018 to 0021 of the Japanese Patent Application Publication No. 2011- The compounds described in paragraphs 0015 to 0018 of Japanese Patent Application Publication No. 257591, the compounds described in paragraphs 0017 to 0021 of Japanese Patent Application Publication No. 2011-191483, the compounds described in paragraphs 0108 to 0116 of Japanese Patent Application Publication No. 2011-145668, and the compounds described in paragraphs 0103 to 0153 of Japanese Patent Application Publication No. 2011-253174, etc.

[0197] In the photosensitive composition of the present invention, the content of free metals not bonded or coordinated with pigments is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less, and preferably substantially free. Based on this state, effects such as stabilization of pigment dispersion (inhibition of aggregation), improvement of spectroscopic properties with improved dispersion, stabilization of curing components, suppression of conductivity changes accompanying the dissolution of metal atoms / metal ions, and improvement of display properties can be expected. Furthermore, the effects described in Japanese Patent Application Publications No. 2012-153796, No. 2000-345085, No. 2005-200560, No. 08-043620, No. 2004-145078, No. 2014-119487, No. 2010-083997, No. 2017-090930, No. 2018-025612, No. 2018-025797, No. 2017-155228, and No. 2018-036521 can also be obtained. Examples of free metals mentioned above include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, and Bi. Furthermore, in the photosensitive composition of the present invention, the content of free halogens not bonded or coordinated with pigments is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less, and practically non-existent is particularly preferred. Examples of halogens include F, Cl, Br, I, and their anions. Methods for reducing free metals and halogens in the photosensitive composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.

[0198] It is preferable that the photosensitive composition of the present invention is substantially free of terephthalate. Here, "substantially free of" means that the content of terephthalate in the total amount of the photosensitive composition is 1000 ppb by mass or less, 100 ppb by mass or less is more preferred, and zero is particularly preferred.

[0199] From an environmental control perspective, the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, is sometimes regulated. In the photosensitive composition of the present invention, when reducing the content of the above-mentioned compounds, the content of perfluoroalkyl sulfonic acids (especially perfluoroalkyl sulfonic acids with a carbon number of 6 to 8) and their salts, and perfluoroalkyl carboxylic acids (especially perfluoroalkyl carboxylic acids with a carbon number of 6 to 8) and their salts, relative to the total solids content of the photosensitive composition, 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. The photosensitive composition of the present invention may also substantially not contain perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts. For example, by using compounds that can serve as substitutes for perfluoroalkyl sulfonic acids and their salts, and compounds that can serve as substitutes for perfluoroalkyl carboxylic acids and their salts, photosensitive compositions that substantially do not contain perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, can also be selected. Examples of compounds that can serve as substitutes for controlled compounds include those excluded from control based on differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. The photosensitive compositions of the present invention may also contain perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, within the maximum permissible range.

[0200] <<Containing Container>> There are no particular restrictions on the container used for the photosensitive composition, and known containers can be used. Furthermore, as a container, for the purpose of preventing impurities from contaminating the raw materials and photosensitive composition, a multi-layered bottle with an inner wall composed of six layers of six different resins, or a bottle with a seven-layer structure of the six resins, is preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container. Furthermore, for the purpose of preventing metal from leaching from the inner wall of the container, improving the storage stability of the photosensitive composition, or inhibiting component deterioration, it is preferable to use a glass or stainless steel container.

[0201] <Preparation Method of Photosensitive Composition> The photosensitive composition of the present invention can be prepared by mixing the aforementioned components. When preparing the photosensitive composition, all components can be dissolved and / or dispersed in a solvent simultaneously to prepare the photosensitive composition, or each component can be appropriately divided into two or more solutions or dispersions as needed, and these can be mixed during use (coating) to prepare the photosensitive composition.

[0202] Furthermore, when preparing photosensitive components, a pigment dispersion process is preferred. In the pigment dispersion process, mechanical forces used to disperse the pigments can include compression, extrusion, impact, shearing, and pitting. Specific examples of such processes include bead milling, sand milling, roller milling, ball milling, coating agitation, microjet milling, high-speed impeller milling, sand mixing, jet mixing, high-pressure wet microparticle formation, and ultrasonic dispersion. Furthermore, when pulverizing pigments in a sand mill (bead mill), it is preferable to treat the process to improve pulverization efficiency by using small-diameter microbeads and increasing the microbead filling rate. Furthermore, after pulverization, it is preferable to remove coarse particles by filtration, centrifugation, or other methods. Furthermore, regarding pigment dispersion processes and dispersers, the processes and dispersers described in "Complete Collection of Dispersion Technology, JOHOKIKO CO.,LTD., July 15, 2005" or "Comprehensive Data Collection on Dispersion Technology and Practical Industrial Applications Centered on Suspension (Solid / Liquid Dispersion Systems), Business Development Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Application Publication No. 2015-157893, are preferable. Additionally, in pigment dispersion processes, particle refinement can be achieved through a salt milling step. For example, the raw materials, equipment, and processing conditions used in the salt milling step can be referenced in Japanese Patent Application Publication Nos. 2015-194521 and 2012-046629.

[0203] When preparing photosensitive components, it is preferable to filter the photosensitive components with a filter for the purpose of removing impurities and reducing defects. As for the filter, any filter that has been used for filtration purposes can be used without particular limitation. Examples of filters using raw materials such as polytetrafluoroethylene (PTFE), 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) are acceptable. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0204] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and further preferably 0.05 to 0.5 μm. As long as the pore size of the filter is within the above range, fine foreign matter can be removed more effectively. For the pore size value of the filter, please refer to the nominal value specified by the filter manufacturer. Various filters supplied by NIHON PALL Corporation (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (Formerly Nippon Mykrolis Corporation), and KITZ MICROFILTER Corporation can be used.

[0205] Furthermore, fibrous filter media are preferred for use as filters. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP series (SBP008, etc.), TPR series (TPR002, TPR005, etc.), and SHPX series (SHPX003, etc.) manufactured by ROKI TECHNO CO.,LTD.

[0206] When using filters, different filters can be combined (e.g., a first filter and a second filter, etc.). In this case, filtration using each filter can be performed only once, or more than twice. Furthermore, filters with different pore sizes can be combined within the aforementioned range. Also, filtration using the first filter can be performed only on the dispersion, and after mixing other components, filtration can be performed using the second filter.

[0207] <Method for Manufacturing a Filter> Next, the method for manufacturing a filter according to the present invention will be described. Examples of filters include color filters, near-infrared cut-off filters, and near-infrared transmittance filters. The method for manufacturing a filter according to the present invention includes the steps of forming a photosensitive composition layer on a support using the photosensitive composition described above, exposing the photosensitive composition layer to light with a wavelength of 300 nm or less in a patterned manner, and developing to remove unexposed portions of the photosensitive composition layer to form pixels. Each step will be described below.

[0208] In the step of forming the photosensitive composition layer of the present invention, the photosensitive composition layer is formed on a support using a photosensitive composition. The support is not particularly limited and can be appropriately selected depending on the application. For example, glass substrates, silicon substrates, etc., are possible, with silicon substrates being preferred. Furthermore, charge-coupled devices (CCDs), complementary metal-oxide-semiconductor (CMOS) films, transparent conductive films, etc., can be formed on the silicon substrate. Also, sometimes partitions is formed on the silicon substrate to isolate each pixel. Furthermore, in order to improve adhesion to the upper layer, prevent material diffusion, or planarize the substrate surface, a base layer can be provided on the silicon substrate. When measured with diiodomethane, a surface contact angle of 20 to 70° is preferred. When measured with water, a surface contact angle of 30 to 80° is preferred. As long as the surface contact angle of the base layer is within the above range, the wettability of the photosensitive composition is good. For example, the surface contact angle of the base layer can be adjusted by adding surfactants or the like.

[0209] Known methods can be used for coating the photosensitive component. Examples include drop casting; slot coating; spraying; roller coating; spin coating; cast coating; slot spin coating; pre-wetting (e.g., the method described in Japanese Patent Application Publication No. 2009-145395); inkjet printing (e.g., on-demand, piezoelectric, thermal), nozzle ejection, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, and other various printing methods; transfer printing using molds, etc.; and nanoimprinting. There are no particular limitations on the applicable methods in inkjet printing. For example, the methods described in "Expansion and Use of Inkjet Printing - Infinite Possibilities Appearing in Patents - Published February 2005, Sumitbe Techon Research Co., Ltd." (especially pages 115-133) or those described in Japanese Patent Application Publication Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-169325 can be cited. Furthermore, regarding the coating method of the photosensitive composition, reference can be made to International Publication Nos. 2017 / 030174 and 2017 / 018419, the contents of which are incorporated herein by reference.

[0210] The photosensitive composition layer formed on the support can be dried (pre-baked). When manufacturing the film using a low-temperature process, pre-baking may not be necessary. When pre-baking is performed, the pre-baking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. For example, the lower limit can be set to 50°C or above, or 80°C or above. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Pre-baking can be performed using a heating plate, oven, or the like.

[0211] Next, the photosensitive composition layer on the support formed above is exposed to light with a wavelength of 300 nm or less in a patterned manner. This allows the exposed portion of the photosensitive composition layer to be cured.

[0212] The light used for exposure can be any light with a wavelength of 300 nm or less, preferably light with a wavelength of 180 to 300 nm. Specifically, examples include light with a wavelength of 248 nm (KrF rays) and light with a wavelength of 193 nm (ArF rays), with light with a wavelength of 248 nm (KrF rays) being preferred.

[0213] Furthermore, during exposure, exposure can be performed by continuously irradiating light or by performing pulsed irradiation (pulse exposure). In addition, pulse exposure refers to an exposure method in which light is repeatedly irradiated and paused in a short period of time (e.g., less than milliseconds) to perform exposure.

[0214] The irradiation dose (exposure dose) is preferably 0.03 to 2.5 J / cm², and more preferably 0.05 to 1.0 J / cm². The oxygen concentration during exposure can be appropriately selected. In addition to exposure under atmospheric conditions, exposure can be performed in low-oxygen environments with an oxygen concentration of less than 19% by volume (e.g., 15% by volume, 5% by volume, or virtually oxygen-free), or in high-oxygen environments with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). Furthermore, the exposure illuminance can be appropriately set, typically within the range of 1000 W / m² to 100000 W / m² (e.g., 5000 W / m², 15000 W / m², or 35000 W / m²). Oxygen concentration and exposure illuminance can be appropriately combined, for example, it can be set to an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m2, an oxygen concentration of 35% by volume and an illuminance of 20,000 W / m2, etc.

[0215] Next, the unexposed portion of the photosensitive composition layer on the photosensitive composition layer after the exposure step is removed by developing. In this way, the unexposed portion of the photosensitive composition layer in the exposure step dissolves into the developing solution, leaving only the photocured portion to form a pixel.

[0216] For example, the temperature of the developer is preferably 20-30°C. The development time is preferably 20-180 seconds. Furthermore, in order to improve the removal of residue, the following steps can be repeated several times: the developer is discarded every 60 seconds, and then a new developer is supplied.

[0217] Developers can include organic solvents and alkaline developers, with alkaline developers being preferred. As an alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferred. Examples of alkaline agents include, for example, organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diethylene glycolamine, diethanolamine, hydroxylamine, 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, or inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. From environmental and safety perspectives, alkaline agents with large molecular weights are preferred. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001–10% by mass, and more preferably 0.01–1% by mass. Furthermore, the developer may further contain surfactants. From the viewpoint of ease of transportation and storage, the developer can be prepared as a concentrate and diluted to the required concentration before use. The dilution ratio is not particularly limited, and can be set in the range of 1.5–100 times. It is also preferable to rinse (wash) with pure water after development. Furthermore, rinsing is preferably performed as follows: while rotating the support on which the developed composition layer has been formed, rinsing solution is supplied to the developed composition layer. It is also preferable to perform rinsing by moving the nozzle discharging the rinsing solution from the center of the support to its periphery. In this case, as the nozzle moves from the center of the support to its periphery, the moving speed of the nozzle can be gradually reduced. By rinsing in this way, in-plane unevenness in rinsing can be suppressed. Alternatively, the same effect can be achieved by gradually reducing the rotational speed of the support while moving the nozzle from the center to the periphery of the support.

[0218] After development, it is preferable to perform additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure treatment and post-baking are used for curing treatment after development to produce fully cured films. For example, the heating temperature during post-baking is preferably 100–240°C, and more preferably 200–240°C. The developed film can be post-baked continuously or intermittently using heating mechanisms such as heating plates, convection ovens (hot air circulating dryers), or high-frequency heaters to achieve the above conditions. When performing additional exposure treatment, it is preferable to use light with a wavelength of 400 nm or less for exposure. Furthermore, the additional exposure treatment can be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0219] The film thickness of the formed pixel can be appropriately adjusted according to the purpose. A film thickness of 20 μm or less is preferred, 10 μm or less is even better, and 5 μm or less is further preferred. A lower limit of 0.1 μm or more is preferred, 0.2 μm or more is even better, and 0.3 μm or more is further preferred.

[0220] It is preferable that the linewidth of the resulting pixel is less than 1.0 μm, even better if it is less than 0.9 μm, further preferable if it is less than 0.8 μm, even more preferable if it is less than 0.7 μm, and best if it is less than 0.6 μm. There is no particular limitation on the lower limit, and it can be set to 0.1 μm or more, or 0.2 μm or more, or 0.3 μm or more, or 0.4 μm or more.

[0221] When forming a plurality of pixels, by repeatedly performing the above steps on each pixel, a filter having a plurality of pixels can be manufactured.

[0222] <Manufacturing Method of Solid State Imaging Element> The manufacturing method of the solid state imaging element of the present invention includes the manufacturing method of the filter of the present invention described above. As for the structure of the solid state imaging element, there is no particular limitation as long as it has a filter and functions as a solid state imaging element; for example, the following structures can be cited.

[0223] That is, the substrate has a transmission electrode formed of a plurality of photodiodes constituting the light-receiving area of ​​a solid-state imaging element (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.), and polysilicon, etc. A light-shielding film with openings only in the light-receiving portion of the photodiodes is provided on the photodiodes and the transmission electrode. An element protective film formed of silicon nitride, etc., is provided on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiodes. A color filter, such as a color filter, is provided on the element protective film. Furthermore, it may also have a structure in which a light-gathering mechanism (e.g., a microlens, etc. The same applies hereinafter) is provided on the element protective film and on the underside (near the substrate) of the filter, or a structure in which a light-gathering mechanism is provided on the filter. The filter may also have a structure in which, for example, each pixel is embedded in a grid-like space separated by partitions. In this case, it is preferable that the refractive index of the partitions is lower than that of each pixel. Examples of camera devices with such a structure include those described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018 / 043654. Furthermore, as shown in Japanese Patent Application Publication No. 2019-211559, an ultraviolet absorption layer can be provided within the structure of the solid-state camera element to improve lightfastness. Camera devices equipped with the solid-state camera element of the present invention can be used not only as digital cameras and electronic devices with camera functions (such as mobile phones), but also as vehicle-mounted cameras and surveillance cameras.

[0224] <Manufacturing Method of Image Display Device> This specification discloses a manufacturing method for an image display device. This manufacturing method includes the method for manufacturing the filter of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescent display devices. Definitions of image display devices and detailed descriptions of various image display devices are described, for example, in "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Publishing Co., Ltd., 1989). Furthermore, liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994). There are no particular limitations on the liquid crystal display devices to which the present invention can be applied; for example, liquid crystal display devices of various types described in "Next-Generation Liquid Crystal Display Technology" can be applied. [Examples]

[0225] Hereinafter, embodiments will be provided to further illustrate the present invention. The materials, amounts, proportions, processing contents, processing order, etc., shown in the following embodiments can be appropriately modified 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.

[0226] <Determination conditions of weight-average molecular weight and number-average molecular weight by gel permeation chromatography> Column type: Columns connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000. Developing solvent: Tetrahydrofuran. Column temperature: 40℃. Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1% by mass). Instrument name: HLC-8220GPC manufactured by Tosoh Corporation. Detector: RI (refractive index). Detector calibration curve. Matrix resin: Polystyrene resin.

[0227] <Manufacturing of Dispersion> A mixture was obtained using the raw materials listed in the mixing table. The obtained mixture was dispersed using an Ultra Apex Mill manufactured by KOTOBUKI KOGYOU CO.,LTD as a circulating dispersion device (bead mill), thereby producing a dispersion.

[0228]

Table 1

[0229] The detailed abbreviations of the raw materials listed in the table above are as follows: [Pigment] PG58: CI Pigment Green 58 (Green Pigment) PG36: CI Pigment Green 36 (Green Pigment) PY185: CI Pigment Yellow 185 (Yellow Pigment) PY215: CI Pigment Yellow 215 (Yellow Pigment) PY129: CI Pigment Yellow 129 (Yellow Pigment) PY139: CI Pigment Yellow 139 (Yellow Pigment) PR254: CI Pigment Red 254 (Red Pigment) PR272: CI Pigment Red 272 (Red Pigment)

[0230] [Dispersing Agent] A-1: ​​Polyethyleneimine (EPOMIN SP-006, manufactured by NIPPON SHOKUBAI CO.,LTD., molecular weight 600, amine value 20mmol / g)

[0231] [Pigment Derivatives] D-1~D-4: Compounds with the following structures [Chemical Formula 27]

[0232] [Dispersant 1] B-1~B-5: Resins with the following structures (polymeric resins. x, y, z in the main chain are molar ratios, and the values ​​in the side chains are the number of repeating units. The values ​​of x, y, z, weight average molecular weight (Mw), and the base values ​​(C=C value) containing ethylene unsaturated bonds are shown in the following tables.)

Chemical Formula 28

Table 2

[0233] [Dispersant 2] E-1: A resin with the following structure (a resin without groups containing vinyl unsaturated bonds. The values ​​indicated in the main chain are molar ratios, and the values ​​indicated in the side chains are the number of repeating units. The weight-average molecular weight is 24,000)

Chemical Formula 29

Chemical Formula 30

[0234] [Solvent] S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Cyclohexanone S-3: Cyclopentanone S-4: Diacetone alcohol S-5: Anisole

[0235] <Manufacturing of Photosensitive Composition> A photosensitive composition was manufactured by mixing the raw materials listed in the table below.

Table 3

[0236] The content of colorant in the total solids of each photosensitive component, the content of polymeric monomer in the total solids of the photosensitive component, the mass parts of polymeric monomer relative to 100 parts by mass of polymeric resin, the basic value of vinyl unsaturated bonds from polymeric monomers in the total solids of the photosensitive component (C=C value 1), and the basic value of vinyl unsaturated bonds from polymeric resins in the total solids of the photosensitive component (C=C value 2) are as follows. Furthermore, C=C value 1 is calculated by dividing the sum of the products of the content of each polymeric monomer in the total solids of the photosensitive component and the C=C value of each polymeric monomer by the total amount of the photosensitive component. Similarly, C=C value 2 is calculated by dividing the sum of the products of the content of each polymeric resin in the total solids of the photosensitive component and the C=C value of each polymeric resin by the total amount of the photosensitive component. Furthermore, the sum of C=C value 1 and C=C value 2 is equivalent to the base value of the solid component of the photosensitive composition containing ethylene unsaturated bonds.

[0237]

Table 5

[0238] The details of the abbreviations for the raw materials used to prepare various photosensitive components are as follows.

[0239] [Polymerizable Monomer] M-1: A compound with the following structure (C=C value: 9.94 mmol / g)

Formula 31

Formula 32

Formula 33

Formula 34

Formula 35

[0240] [Resin] C-1: Resin with the following structure (polymeric resin. Values ​​indicated in the main chain are molar ratios. Weight-average molecular weight is 11000, C=C value: 1.44 mmol / g)

Chemical Formula 36

Chemical Formula 37

[0241] [Photopolymerization Initiator] I-1: Irgacure OXE02 (manufactured by BASF, oxime compound)

[0242] [Surfactant] W-1: A compound with the following structure (fluorine-based surfactant, weight average molecular weight 14000, the percentage of repeating units is in moles)

Chemical Formula 38

[0243] [Polymerization Inhibitor] Q-1: p-Methoxyphenol

[0244] [Solvent] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0245] <Evaluation of Photolithography> On an 8-inch (203.2 mm) silicon wafer with an attached substrate coating, the above-obtained photosensitive components were spin-coated using an Act8 wafer manufactured by OKYO Electron Limited to achieve a film thickness of 0.4 μm. The substrate layer was then formed by heating at 100°C for 2 minutes using a hot plate. Next, the substrate layer was exposed to 35000 W / m² of 248 nm light (KrF rays) at an exposure dose of 200 mJ / cm² through a mask with a 0.7 μm square pattern or a 0.6 μm square pattern. Following this, the exposed substrate layer was spray-developed for 60 seconds at 23°C using a 0.3% (w / w) aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. Pixels were then formed by rinsing with pure water using a rotating spray. The obtained pixels were observed at 20,000x magnification using a scanning electron microscope (S-4800H, Hitachi High-Tech Corporation). Based on the observed images, photoresistivity was evaluated according to the following criteria. Three photoresistivity tests were performed on each sample, and the results were combined for judgment. Evaluation results using a mask with a 0.7μm square pattern are recorded in the photoresistivity 1 column, and evaluation results using a mask with a 0.6μm square pattern are recorded in the photoresistivity 2 column. (Evaluation Criteria) 5: Good straightness of pixel edges, no residue between pixels. 4: Good straightness of pixel edges, little residue between pixels. 3: Slightly rounded pixel edges, little residue between pixels. 2: Rounded pixel edges, much residue between pixels. 1: Pixels cannot be formed.

[0246]

Table 6

[0247] As shown in the table above, the photolithography of the embodiment is well evaluated, and pixels can be formed even when a mask with a pattern of 0.6 μm square is used. Furthermore, there is little residue between pixels.

[0248] In the photosensitive compositions of Examples 25 to 43, the same effect can be obtained even if the surfactant W-1 is replaced with surfactants W-2 to W-44 as shown below.

[0249] W-2: FZ-2122 (manufactured by Dow Corning Toray Co., Ltd., polysiloxane surfactant) W-3: BYK-322 (manufactured by BYK-Chemie GmbH, polysiloxane surfactant) W-4: BYK-323 (manufactured by BYK-Chemie GmbH, polysiloxane surfactant) W-5: BYK-330 (manufactured by BYK-Chemie GmbH, polysiloxane surfactant) W-6: BYK-3760 (manufactured by BYK-Chemie GmbH, polysiloxane surfactant) W-7: BYK-UV3510 (manufactured by BYK-Chemie GmbH, polysiloxane surfactant) W-8: KF-6001 (Shin-Etsu Chemical Co., Ltd., polysiloxane surfactant) W-9: MEGAFACE F-477 (DIC Corporation, fluorinated surfactant) W-10: MEGAFACE F-554 (DIC Corporation, fluorinated surfactant) W-11: MEGAFACE F-555-A (DIC Corporation, fluorinated surfactant) W-12: MEGAFACE F-556 (DIC Corporation, fluorinated surfactant) W-13: MEGAFACE F-557 (DIC Corporation, fluorinated surfactant) W-14: MEGAFACE F-558 (DIC Corporation, fluorinated surfactant) W-15: MEGAFACE F-559 (DIC Corporation, fluorinated surfactant) W-16: MEGAFACE F-560 (DIC Corporation, fluorinated surfactant) W-17: MEGAFACE F-561 (DIC Corporation, fluorinated surfactant) W-18: MEGAFACE F-563 (DIC Corporation, fluorinated surfactant) DIC Corporation, fluorinated surfactants) W-19: MEGAFACE F-565 (DIC Corporation, fluorinated surfactants) W-20: MEGAFACE F-568 (DIC Corporation, fluorinated surfactants) W-21: MEGAFACE F-575 (DIC Corporation, fluorinated surfactants) W-22: MEGAFACE R-01 (DIC Corporation, fluorinated surfactants) W-23: MEGAFACE R-40 (DIC Corporation, fluorinated surfactants)Fluorine-based surfactants) W-24: MEGAFACE R-40-LM (DIC Corporation, fluorine-based surfactant) W-25: MEGAFACE R-41 (DIC Corporation, fluorine-based surfactant) W-26: MEGAFACE R-41-LM (DIC Corporation, fluorine-based surfactant) W-27: MEGAFACE R-94 (DIC Corporation, fluorine-based surfactant) W-28: MEGAFACE DS-21 (DIC Corporation, fluorine-based surfactant) W-29: MEGAFACE RS-43 (DIC Corporation, fluorine-based surfactant) W-30: MEGAFACE RS-72-K (DIC Corporation, fluorine-based surfactant) W-31: MEGAFACE RS-90 (DIC Corporation, fluorine-based surfactant) W-32: MEGAFACE TF-1956 (DIC Corporation, fluorine-based surfactant) W-33: Futurgent 208G (NEOS COMPANY LIMITED, fluorinated surfactant) W-34: Futurgent 215M (NEOS COMPANY LIMITED, fluorinated surfactant) W-35: Futurgent 245F (NEOS COMPANY LIMITED, fluorinated surfactant) W-36: Futurgent 601AD (NEOS COMPANY LIMITED, fluorinated surfactant) W-37: Futurgent 601ADH2 (NEOS COMPANY LIMITED, fluorinated surfactant) W-38: Futurgent 602A (NEOS COMPANY LIMITED, fluorinated surfactant) W-39: Futurgent 610FM (NEOS COMPANY LIMITED, fluorinated surfactant) W-40: Futurgent 710FL (NEOS COMPANY LIMITED, fluorinated surfactant) W-41: Futurgent 710FM (NEOS COMPANY LIMITED, fluorinated surfactant) W-42: Futurgent 710FS (NEOS COMPANY LIMITED, fluorinated surfactant) W-43: Futurgent FTX-218 (NEOS COMPANY LIMITED,Fluorinated surfactants) W-44: PF-6320 (manufactured by OMNOVA SOLUTIONS INC., fluorinated surfactants).

[0250] (Example 1001) A green photosensitive composition was coated onto a silicon wafer using spin coating to achieve a film thickness of 0.4 μm. Next, the wafer was heated at 100°C for 2 minutes using a hot plate. Then, exposure was performed using a KrF scanning exposure machine, irradiating the wafer with light (KrF rays) at a wavelength of 248 nm through a mask having a Bayer pattern formed with pixels (patterns) of 0.7 μm square, at an exposure dose of 200 mJ / cm². Next, development was performed using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds. Afterwards, the wafer was rinsed by a spin spray and further washed with pure water. Finally, the wafer was heated at 200°C for 5 minutes using a hot plate, thereby forming green pixels. Using the same process, the red and blue photosensitive components were also patterned to sequentially form red and blue pixels, thereby forming a color filter with green, red, and blue pixels. In this color filter, the green pixels were formed in a Bayer pattern, and in the adjacent areas, the red and blue pixels were formed in island patterns. The obtained color filter was assembled into a solid-state imaging element according to known methods. This solid-state imaging element has better image recognition capabilities. Furthermore, the green photosensitive component used was the photosensitive component of Example 31. The red photosensitive component used was the photosensitive component of Example 36. The blue photosensitive component used the composition shown below.

[0251] -Blue Photosensitive Composition- A blue photosensitive composition was prepared by mixing and stirring the following components and then filtering them through a nylon filter (made by NIHON PALL LTD.) with a pore size of 0.45 μm. Blue pigment dispersion 44.9 parts by mass; resin 101 parts by mass 2.1 parts by mass; polymeric compound 101 parts by mass 1.5 parts by mass; polymeric compound 102 parts by mass 0.7 parts by mass; photopolymerization initiator 101 parts by mass 0.8 parts by mass; surfactant 101 parts by mass 4.2 parts by mass; PGMEA 45.8 parts by mass

[0252] The raw materials used in the blue photosensitive composition are as follows.

[0253] A blue pigment dispersion was obtained by mixing and dispersing a mixture of 9.7 parts by weight of CI pigment blue 15:6, 2.4 parts by weight of CI pigment violet 23, 5.5 parts by weight of dispersant (Disperbyk-161, manufactured by BYK-Chemie GmbH), and 82.4 parts by weight of PGMEA for 3 hours using a bead mill (0.3 mm diameter zirconia beads). Subsequently, the dispersion was further performed using a NANO-3000-10 high-pressure disperser (manufactured by Japan BEE Co., Ltd.) with a pressure of 2000 kg / cm³ and a flow rate of 500 g / min. This dispersion process was repeated 10 times to obtain the blue pigment dispersion.

[0254] Resin 101: A 40% by mass PGMEA solution of a resin with the following structure (the values ​​indicated in the main chain are moles. The weight average molecular weight is 11000) [Chemical Formula 39] Polymerizable Compound 101: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) Polymerizable Compound 102: A compound with the following structure [Chemical Formula 40] Photopolymerization Initiator 101: Irgacure OXE02 (manufactured by BASF) Surfactant 101: A 1% by mass PGMEA solution of a compound with the following structure (weight average molecular weight 14000, where the percentage of repeating units in the following formula is moles) [Chemical Formula 41]

Claims

1. A photosensitive composition for exposure to light with a wavelength of less than 300 nm and comprising: a colorant A, a photopolymerization initiator B, a polymerizable monomer C having a group containing an ethylene unsaturated bond, and a polymerizable resin D having a group containing an ethylene unsaturated bond, wherein the colorant A has a content of more than 50% by mass in the total solids content of the photosensitive composition, the polymerizable monomer C has a content of more than 4% by mass in the total solids content of the photosensitive composition, and the polymerizable monomer C contains 25 to 75 parts by mass relative to 100 parts by mass of the polymerizable resin D, the photosensitive composition comprises two or more of the polymerizable resin D, and the polymerizable resin D comprises a resin containing a repeating unit represented by the following formula (A-1-1) and a repeating unit represented by the following formula (A-1-2); 1. (In formula (A-1-1), X1 represents a trivalent linkage group, L1 represents a single bond or a divalent linkage group, and Y1 represents a group containing an ethylene unsaturated bond); 1. (In formula (A-1-2), X2 represents a trivalent linker, L2 represents a single bond or a divalent linker, and W1 represents a graft chain).

2. The photosensitive composition as described in claim 1, wherein the aforementioned color material A comprises a colored color material.

3. The photosensitive composition as described in claim 1 or claim 2, wherein the aforementioned polymeric monomer C comprises a 2-8 functional polymeric monomer containing 2 to 8 groups with ethylene unsaturated bonds.

4. The photosensitive composition as described in claim 1 or claim 2, wherein the base value of the total solids content of the aforementioned photosensitive composition derived from the aforementioned polymeric monomer C containing ethylene unsaturated bonds is 0.01~8 mmol / g.

5. The photosensitive composition as described in claim 1 or claim 2, wherein the base value of the total solids content of the aforementioned photosensitive composition derived from the aforementioned polymeric resin D containing vinyl unsaturated bonds is 0.001~5 mmol / g.

6. The photosensitive composition as described in claim 1 or claim 2, wherein the total stoichiometry of the polymeric monomer C and the polymeric resin D in the total solids composition of the photosensitive composition is 5 to 45 by mass.

7. The photosensitive composition as described in claim 1 or claim 2, wherein the content of the aforementioned photopolymerization initiator B in the total solids content of the aforementioned photosensitive composition is 1 to 10 by mass.

8. The photosensitive composition as described in claim 1 or claim 2, used to form red or green pixels of a color filter.

9. The photosensitive composition as described in claim 1 or claim 2, used in a solid-state imaging element.

10. The photosensitive composition as claimed in claim 1 or claim 2, wherein the base value of the solid component of the aforementioned photosensitive composition containing vinyl unsaturated bonds is 0.01 to 1.55 mmol / g.

11. The photosensitive composition as described in claim 1 or claim 2, wherein the base value of the total solids content of the aforementioned photosensitive composition derived from the aforementioned polymeric resin D containing vinyl unsaturated bonds is 0.001 to 0.10 mmol / g.

12. A method for manufacturing a filter, comprising: The steps are: forming a photosensitive composition layer on a support using any one of claims 1 to 11; exposing the aforementioned photosensitive composition layer to light with a wavelength of 300 nm or less in a patterned manner; and developing to remove the unexposed portion of the aforementioned photosensitive composition layer to form a pixel.

13. The method of manufacturing a filter as claimed in claim 12, wherein the light irradiated onto the aforementioned photosensitive composition layer with a wavelength of 300 nm or less is light with a wavelength of 248 nm.

14. A method for manufacturing a solid-state imaging element, comprising the method for manufacturing the filter described in claim 12 or claim 13.