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. Prior Technology

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

[0003] For example, color filters can be manufactured using photosensitive compositions containing colorants, photopolymerization initiators, and polymerizable monomers.

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

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

[0006] In recent years, there has been ongoing research into miniaturization and high resolution of solid-state imaging devices incorporating color filters and other light filters. Therefore, research is being conducted on pixel miniaturization for these light filters.

[0007] Furthermore, in recent years, there has been a growing demand for miniaturization and thin-film technology in solid-state imaging devices. Therefore, there has been a growing demand for thinner films containing color materials, such as color filters, used in solid-state imaging devices. To maintain the desired spectral performance and achieve thin-film technology, 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, leading to a tendency for 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 opening size of the mask narrows, the amount of exposure light reaching the photosensitive composition in the exposed area decreases, thus failing to cure sufficiently to the bottom of the film (support side), easily resulting in insufficient adhesion between the obtained pixels and the support.

[0009] While increasing the exposure during pixel formation using photolithography can fully harden the film during exposure, the unexposed areas around the mask opening also harden, leading to 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, the unexposed areas around the opening tend to harden further due to standing wave effects, resulting in pixel linewidths that are often coarser than the mask opening size. These problems are 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 component 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 objectives can be achieved by configuring the invention as follows, thus completing the present invention. Therefore, the present invention provides the following. <1> A photosensitive composition for exposure to light with wavelengths below 300 nm and comprising: 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 content of the aforementioned colorant A in the total solids composition of the aforementioned photosensitive component is greater than 50% by mass. The content of the polymerizable monomer C in the total solids of the above-mentioned photosensitive composition is 4% by mass or more. Relative to 100 parts by mass of the polymeric resin D, it contains 5 to 200 parts by mass of the polymeric monomer C. <2> like <1> The photosensitive component, wherein The aforementioned color material A includes colored color materials. <3> like <1> or <2> The photosensitive component, wherein The polymerizable monomer C described above is a 2-8 functional polymerizable monomer containing 2 to 8 groups with ethylene unsaturated bonds. <4> like <1> to <3> The photosensitive composition described in any one of the claims, wherein The total solids content of the above-mentioned photosensitive composition, including the amount of vinyl unsaturated bonds in the polymeric monomer C, ranges from 0.01 to 8 mmol / g. <5> like <1> to <4> The photosensitive composition described in any one of the claims, wherein The base value of the total solids content of the above-mentioned photosensitive composition derived from the above-mentioned polymeric resin D containing ethylene unsaturated bonds is 0.001~5 mmol / g. <6> like <1> to <5> The photosensitive composition described in any one of the claims, 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> like <1> to <6> The photosensitive composition described in any one of the claims, wherein The total solids composition of the above-mentioned photosensitive components contains a mass ratio of 5 to 45 for the polymeric monomer C and the polymeric resin D. <8> like <1> to <7> The photosensitive composition described in any one of the claims, wherein The content of the above-mentioned photopolymerization initiator B in the total solids content of the above-mentioned photosensitive composition is 1 to 10 by mass. <9> like <1> to <8> The photosensitive composition described in any one of the claims is used to form the red or green pixels of the color filter. <10> like <1> to <9> The photosensitive composition described in any one of the claims is used in a solid-state imaging element. <11> A method for manufacturing a filter, comprising: use <1> to <10> The step of forming a photosensitive composition layer on a support according to any one of the claims; The steps of exposing the above-mentioned photosensitive composition layer to light with a wavelength of less than 300 nm in a patterned manner; and The step of developing and removing the aforementioned photosensitive component layer from the unexposed areas to form pixels. <12> like <11> The method for manufacturing the filter, wherein The light with a wavelength of 300 nm or less that irradiates the above-mentioned photosensitive composition layer is light with a wavelength of 248 nm. <13> A method for manufacturing a solid-state imaging element, comprising: <11> or <12> The method for manufacturing the filter. [Invention Effects]

[0012] According to the present invention, a photosensitive component 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

[0013] The present invention will now 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 this specification, the designation of groups (atomic groups) includes both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (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 represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula. 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 pigment has a solubility of less than 0.1g in 100g of water at 23°C and less than 0.01g in 100g of propylene glycol monomethyl ether acetate at 23°C. In this specification, the symbols (such as A, B, C, and D) attached before or after the name are used to distinguish the constituent elements and do not limit the types, number, or quality of the constituent elements. In this specification, the term "step" includes not only independent steps, but also steps that achieve the desired effect, even if they cannot be clearly distinguished from other steps.

[0014] <Photosensitive components> The photosensitive composition of the present invention is for exposure to light with a wavelength below 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. Colorant A contains more than 50% by mass in the total solids of the photosensitive composition. The content of polymerizable monomer C in the total solids composition of the photosensitive component is 4% by mass or more. Relative to 100 parts by mass of polymeric resin D, it contains 5 to 200 parts by mass of polymeric 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 photomicrography is 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 to light with a wavelength of less than 300 nm. Since light with wavelengths below 300 nm has high energy density, irradiating the photosensitive composition of the present invention with light with wavelengths below 300 nm can instantaneously generate a large number of active species such as free radicals 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 deactivation caused by oxygen, the polymerizable monomers and polymerizable resins 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 polymerizable monomer C account for 4% or more of the total solids content of the photosensitive composition and containing 5 to 200 parts by mass 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 C=C value (hereinafter also referred to as the C=C value) of the total solids content of the photosensitive composition of the present invention, which comprises vinyl unsaturated bonds from polymeric monomer C, 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 total solids content of the photosensitive composition from polymeric monomer C is within the above range, high-density three-dimensional cross-linking can be formed by exposure, and fine patterning is effective. Furthermore, the C=C value of the total solids content of the photosensitive composition from polymeric monomer C 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. Also, the C=C value of the polymeric resin refers to the molar amount of C=C groups per 1g of solids of the polymeric resin. The C=C value of a polymeric resin can be calculated as follows: The low-molecular-weight component (a) of the C=C group is extracted from the polymeric resin by alkali treatment, and the content of this low-molecular-weight component (a) relative to the C=C group of the polymeric resin 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 polymeric resin by alkali treatment, the value determined by NMR (nuclear magnetic resonance) is used. The C=C value of a 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 excellent curing properties after exposure effectively amplify the difference in alkaline developability between the exposed and unexposed areas, 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 is preferably used as a photosensitive composition for a filter. Examples of filters include color filters, near-infrared cutoff filters, and near-infrared transmittance filters, with color filters being preferred.

[0022] As a color filter, an example is a filter with colored pixels. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0023] As a near-infrared cutoff filter, an example is a filter that blocks at least a portion of the wavelengths of light in the near-infrared region. 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. Also, 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, the ratio of absorbance Amax at the maximum absorption wavelength to absorbance A550 at 550 nm (absorbance Amax / absorbance A550) is preferably 20~500, even better 50~500, further better 70~450, and best 100~400.

[0024] As a near-infrared transmission filter, an example is a filter that blocks at least a portion of visible light while allowing at least a portion of near-infrared light to pass through. 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. A near-infrared transmission filter that satisfies any one of the following spectral characteristics (IR1) to (IR5) is preferred. (IR1): A filter whose maximum transmittance in the wavelength range of 400~640nm is less than 20% (preferably less than 15%, more preferably less than 10%) and whose minimum transmittance in the wavelength range of 800~1500nm is more than 70% (preferably more than 75%, more preferably more than 80%). (IR2): A filter whose maximum transmittance in the wavelength range of 400~750nm is less than 20% (preferably less than 15%, more preferably less than 10%) and whose minimum transmittance in the wavelength range of 900~1500nm is more than 70% (preferably more than 75%, more preferably more than 80%). (IR3): A filter whose maximum transmittance in the wavelength range of 400~830nm is less than 20% (preferably less than 15%, more preferably less than 10%) and whose minimum transmittance in the wavelength range of 1000~1500nm is more than 70% (preferably more than 75%, more preferably more than 80%). (IR4): A filter with a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400~950nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1100~1500nm. (IR5): A filter whose maximum transmittance in the wavelength range of 400~1050nm is less than 20% (preferably less than 15%, more preferably less than 10%) and whose minimum transmittance in the wavelength range of 1200~1500nm 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 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 in 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 further preferably 15% by mass or less.

[0027] The components of the photosensitive composition used in this invention will be described below.

[0028] <<Color material>> The photosensitive composition of the present invention contains a colorant A (hereinafter referred to as the colorant). The colorant can be a pigment or a dye. Pigments and dyes can be used simultaneously. Furthermore, the pigment can be any of inorganic pigments or organic pigments. Also, the pigment can 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 1-200 nm. A lower limit of 5 nm or more is preferred, and 10 nm or more is even better. An upper limit of 180 nm or less is preferred, 150 nm or less is even better, and 100 nm or less is further 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 colorants that contain pigments. A pigment content of 50% or more by mass is preferred, 70% or more by mass is even better, 80% or more by mass is further better, and 90% or more by mass is exceptionally good.

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

[0032] (color material) As color materials, examples include those with extremely high absorption wavelengths in the range of 400 to 700 nm. Examples include yellow, orange, red, green, purple, and blue color materials. Specific examples of color materials include those shown below.

[0033] Colorimetric Index (CI) for 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, 127, 1 Yellow pigments in the following series: 28, 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 pigments 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73. CI Pigment 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 Red pigments in the following colors: 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. CI pigments include green pigments 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine), 65 (phthalocyanine), and 66 (phthalocyanine). CI pigments include purple 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), and 61 (a type of galaxy). CI pigment blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo), 88 (methylene) and other blue pigments.

[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. Specific examples include the compound described in International Patent Application Publication No. 2015 / 118720. Additionally, as a green pigment, compounds described in Chinese Patent Application No. 106909027, phthalocyanine compounds with phosphate esters as ligands described in International Patent Application 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., can also be used.

[0035] Furthermore, aluminum phthalocyanine compounds containing 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 0016-0022 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 azotized compounds described in Japanese Patent Application Publication No. 2012-229344. Compounds, including the red pigment described in Japanese Patent No. 6516119, the red pigment described in Japanese Patent No. 6525101, the brominated diketone pyrrolopyrrole compound described in paragraph 0229 of Japanese Patent Application Publication No. 2020-090632, the anthraquinone compound described in Korean Patent Publication No. 10-2019-0140741, the anthraquinone compound described in Korean Patent Publication No. 10-2019-0140744, and the perylene compound described in Japanese Patent Application Publication No. 2020-079396, etc. Furthermore, as a red pigment, 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 diketone pyrrolopyrrole 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 and 0137-0276 of Japanese Patent Application Publication No. 2017-171912, compounds described in paragraphs 0010-0062 and 0138-0295 of Japanese Patent Application Publication No. 2017-171913, compounds described in paragraphs 0011-0062 and 0139-0190 of Japanese Patent Application Publication No. 2017-171914, and compounds described in paragraphs 0010-0065 and 0142-0222 of Japanese Patent Application Publication No. 2017-171915 are also applicable. The compounds described in the following categories: Quinoline yellow compounds described in paragraphs 0011-0034 of Japanese Patent Application Publication No. 2013-054339; quinoline yellow compounds described in paragraphs 0013-0058 of Japanese Patent Application Publication No. 2014-026228; isoindoline compounds described in Japanese Patent Application Publication No. 2018-062644; quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-203798; quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-062578; quinoline yellow compounds described in Japanese Patent Application Publication No. 6432077; quinoline yellow compounds described in Japanese Patent Application Publication No. 6432076; and quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-155881. Quinoline yellow compounds, quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-111757, quinoline yellow compounds described in Japanese Patent Application Publication No. 2018-040835, quinoline yellow compounds described in Japanese Patent Application Publication No. 2017-197640, quinoline yellow compounds described in Japanese Patent Application Publication No. 2016-145282, quinoline yellow compounds described in Japanese Patent Application Publication No. 2014-085565, quinoline yellow compounds described in Japanese Patent Application Publication No. 2014-021139, quinoline yellow compounds described in Japanese Patent Application Publication No. 2013-209614, quinoline yellow compounds described in Japanese Patent Application Publication No. 2013-209435, quinoline yellow compounds described in Japanese Patent Application Publication No. 2013-18 The quinoline yellow compounds described in Japanese Patent Application Publication No. 1015, 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, Japanese Patent Application Publication No. 2008-074986, and Japanese Patent Application Publication No. 2008-074985.The following compounds are described in Japanese Patent Application Publication No. 2008-050420, Japanese Patent Application Publication No. 2008-031281, Japanese Patent Application 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 No. 6607427. Furthermore, from the viewpoint of improving color value, polymerizing these compounds is also preferable. Moreover, compounds represented by formula (QP1) and compounds represented by formula (QP2) can also be used as yellow pigments. , [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 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, diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used.

[0042] Regarding the optimal diffraction angles of various pigments, reference can be made to 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 colorants. There are no particular restrictions on the type of dye 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. Additionally, pigment polymers can also be used as dyes. Pigment polymer systems with two or more pigment structures per molecule are preferred, especially three or more. There is no particular upper limit, and 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. A weight-average molecular weight (Mw) of 2000 to 50000 is preferred for pigment polymers. 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 the 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 15-100 parts by weight relative to 100 parts by weight of green pigment, more preferably 20-70 parts by weight, and further preferably 25-60 parts by weight. It is preferable that the green pigments are CI pigment green 7, 36, 58, 59, or 63, with CI pigment green 36 or 58 being more preferred. It is preferable that the yellow pigments are CI pigment yellow 129, 138, 139, 150, 185, 215, 231, or 233, with CI pigment yellow 129, 139, 185, or 215 being more preferred.

[0045] Furthermore, when using the photosensitive composition of the present invention 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 (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) contains red and blue pigments. (Bk2) contains red, blue and yellow pigments. (Bk3) contains red, blue, yellow and purple pigments. (Bk4) contains red, blue, yellow, purple and green pigments. (Bk5) contains 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. White pigments containing titanium atoms are preferred, with titanium dioxide being even more desirable. 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 desirable. Additionally, titanium dioxide, as described in "Titanium Oxide Properties and Application Technology, Kiyono Kagaku, pp. 13-45, published June 25, 1991, Gihodo Publishing," can also be used as a white pigment.

[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 multiple 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) There are no particular limitations on the use of black pigments; known materials can be used. For example, as inorganic black pigments, carbon black, titanium black, and graphite can be cited, 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 inhibit 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 black pigments, pigments with colorimetric index (CI) of 1 and 7 can be cited. Regarding titanium black, it is preferable that both the primary particle size and the average primary particle size of each particle are small. Specifically, an average primary particle size of 10-45 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 (such as Lumogen Black FK4280) 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 colorants are preferably pigments, and organic pigments are even better. Furthermore, near-infrared absorbing colorants are preferably compounds with 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 above absorbance ratio is within the above range, it can be used as a near-infrared absorbing colorant with excellent visible transparency and near-infrared shielding properties. In addition, the values ​​of the maximum absorption wavelength and absorbance at each wavelength of the near-infrared absorbing colorant are obtained from the absorption spectrum of the film formed using a photosensitive composition containing the near-infrared absorbing colorant.

[0052] There are no particular limitations on the types of near-infrared absorbing colorants, but 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 0016-0058 of Japanese Patent Application Publication No. 2009-263614, those described in paragraphs 0037-0052 of Japanese Patent Application Publication No. 2011-068731, and those described in paragraphs 0010-0033 of International Patent Publication No. 2015 / 166873. Examples of compounds that can be cited as squaric acid cyanine compounds include those described in paragraphs 0044-0049 of Japanese Patent Application Publication No. 2011-208101, those described in paragraphs 0060-0061 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 0048-0063. 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, it is also possible to use the succinic acid 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. The following compounds are described in Japanese Patent No. 5810604, International Publication No. 2017 / 213047 (paragraphs 0090-0107), Japanese Patent Application Publication No. 2018-054760 (paragraphs 0019-0075), and Japanese Patent Application Publication No. 2018-040955 (paragraphs 0078-0082). The following compounds contain pyrrole rings: those described in paragraphs 0043 to 0069 of Japanese Patent Application Publication No. 2018-002773; those containing squaric acid compounds with an aromatic ring at the α-position of acetylamine as described in paragraphs 0024 to 0086 of Japanese Patent Application Publication No. 2018-041047; those containing acetylamine-linked squaric acid compounds as described in Japanese Patent Application Publication No. 2017-179131; and those containing pyrrole bimorphic squaric acid compounds as described in Japanese Patent Application Publication No. 2017-141215. Compounds with an acid-cyanine skeleton or a ketone-onium skeleton, dihydrocarbazole bitype squaric acid-cyanine compounds disclosed in Japanese Patent Application Publication No. 2017-082029, asymmetric compounds disclosed in paragraphs 0027 to 0114 of Japanese Patent Application Publication No. 2017-068120, pyrrole ring-containing compounds (carbazole type) disclosed in Japanese Patent Application Publication No. 2017-067963, and phthalocyanine compounds disclosed 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 colorant is preferably 200-2000 parts by mass relative to 100 parts by mass of polymeric monomer. The lower limit is preferably 250 parts by mass or more, more preferably 300 parts by mass or more, and further 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, further preferably 800 parts by mass or less, and especially 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 Initiators>> The photosensitive composition of the present invention contains a photopolymerization initiator B (hereinafter referred to as the photopolymerization initiator). There are no particular limitations on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, a compound that is photosensitive to light in the ultraviolet to visible regions is preferred. A photoradical polymerization initiator is preferred.

[0058] Examples of photopolymerization initiators 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, onium 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] Commercially available α-hydroxy ketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-amino ketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), and 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 Application 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 0025-0038 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 photopolymerization initiators, oxime compounds with 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 containing fluorine atoms can also be used as photopolymerization initiators. Specific examples of oxime compounds containing 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] Nitro-containing oxime compounds can be used as photopolymerization initiators. It is also preferable that the nitro-containing oxime compound is a dimer. Specific examples of nitro-containing 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 Publication 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] As photopolymerization initiators, oxime compounds with hydroxyl substituents bonded to the carbazole backbone can also be used. 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, alkylsulfinyl, arylsulfinyl, 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, phosphino, 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; Among them, at least one of RX10 to RX14 is an electron-withdrawing group.

[0069] Examples of electron-withdrawing groups 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 better, 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 the 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 this invention, but the invention is not limited to these.

[0073] [Chemical Formula 5] [Chemical Formula 6]

[0074] Oxidime compounds are preferably those with maximum absorption wavelengths in the range of 350–500 nm, and even more preferably those with maximum absorption wavelengths in the range of 360–480 nm. Furthermore, from a sensitivity point of view, it is preferable for oxime compounds to have high molar absorptivity at wavelengths of 365 nm or 405 nm, with 1,000–300,000 being more preferred, 2,000–300,000 being further preferred, and 5,000–200,000 being particularly preferred. 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) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0075] As photopolymerization initiators, photoradical polymerization initiators with two or more functionalities can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, when using compounds with asymmetric structures, crystallinity decreases while 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 No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. 2015 / 004565, Japanese Patent Application Publication No. 2016-532675 (paragraphs 0407-0412), and International Publication No. 2017 / 033680 (paragraphs 0039-0055), as well as compounds described in Japanese Patent Application Publication No. 2013-522445. (E) and compound (G), Cmpd1 to 7 as disclosed in International Publication No. 2016 / 034963, oxime ester photoinitiators as disclosed in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as disclosed in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as disclosed in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342 (A), and oxime ester photoinitiators as disclosed in Japanese Patent Application Publication No. 6469669, etc.

[0076] The content of the photopolymerization initiator in the total solids of the photosensitive composition is preferably 1-10% 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 used simultaneously. When two or more types are used simultaneously, the total content within the above range is preferred.

[0077] <<Polymerizable Monomers>> 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. A free radical polymerizable monomer system is preferred for use in the present invention.

[0078] The molecular weight of the polymerizable monomer is preferably 100 or higher and less than 3000. An upper limit of less than 2000 is more preferred, and less than 1500 is even more preferred. A lower limit of 150 or higher is more preferred, and more than 250 is even more preferred. Compounds in which the polymerizable monomer does not exhibit a specific molecular weight distribution are also preferred.

[0079] The polymerizable monomer preferably comprises 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 further preferably a 2-6 functional polymerizable monomer containing 2 to 6 groups with vinyl unsaturated bonds. Furthermore, the polymerizable monomer preferably comprises a 1-10 functional (meth)acrylate compound, more preferably a 2-8 functional (meth)acrylate compound, and further 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 1.0~15.0 mmol / g. The lower limit is preferably above 1.5 mmol / g, and more preferably above 2.0 mmol / g. The upper limit is preferably below 14.0 mmol / g, and more preferably below 12.0 mmol / g.

[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 these (meth)acrylic acid groups linked via ethylene glycol and / or propylene glycol residues (e.g., by SARTOMER) The commercially available SR454 and SR499 from Company, Inc. 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 monomers 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, ethylene oxide isocyanurate modified tri(meth)acrylate, and 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 areas 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 0.1~40 mgKOH / g, more preferably 5~30 mgKOH / g. If the acid value of the polymerizable monomer is 0.1 mgKOH / g or higher, its solubility in the developer is good; if it is 40 mgKOH / g or lower, it is advantageous for manufacturing or handling.

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

[0085] Polymerizable monomers with a basal framework are preferred. By using polymerizable monomers with a basal framework for adsorption with organic pigments, the curing degree based on exposure can be improved, thereby achieving the effects of the present invention more significantly. Polymerizable monomers with a basal framework and difunctionality are preferred.

[0086] Examples of polymerizable monomers with a basal framework 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 carbon atom end is bonded to R.

[0090] [Chemical Formula 9]

[0091] In the above formula, n ranges from 0 to 14, and m ranges from 1 to 8. Within a molecule, there can be multiple R and T values ​​that can be the same or different. In each compound represented by the above formulas (MO-1) to (MO-6), at least one of the complex Rs represents -OC(=O)CH=CH2, -OC(=O)C(CH3)=CH2, -NHC(=O)CH=CH2 or -NHC(=O)C(CH3)=CH2. As a specific example of a polymeric compound represented by the above formulas (MO-1) to (MO-6), the compound described in paragraphs 0248 to 0251 of Japanese Patent Application Publication No. 2007-269779 can be cited.

[0092] It is also preferable to use compounds with a caprolactone structure as polymerizable monomers. Compounds with a caprolactone structure are preferably those 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] In formula (Z-2), R1 represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents a bond.

[0096] [Chemical Formula 12] In formula (Z-3), R1 represents a hydrogen atom or a methyl group, and "*" represents a bond.

[0097] Commercially available monomers with 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 sum of all 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 sum of all n groups is an integer from 0 to 60.

[0101] In formula (Z-4), it is preferable for m to be an integer from 0 to 6, and even better for m to be an integer from 0 to 4. Furthermore, it is preferable for the sum of all m to be an integer from 2 to 40, even better for m to be an integer from 2 to 16, and best for m to be an integer from 4 to 8. In formula (Z-5), it is preferable for n to be an integer from 0 to 6, and even better for n to be an integer from 0 to 4. Furthermore, it is preferable for the sum of all n to be an integer from 3 to 60, even better for n to be an integer from 3 to 24, and best for n to be an integer from 6 to 12. Furthermore, the morphology of the terminal bond of the oxygen atom on the X side in formula (Z-4) or formula (Z-5) to -((CH2)yCH2O)- or -((CH2)yCH(CH3)O)- is preferred.

[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 more preferably 15% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 68% by mass or more, further preferably 10% by mass or more, and even more preferably 12% by mass or more.

[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, with 10 to 100 parts by weight being preferred, 15 to 90 parts by weight being even better, 20 to 80 parts by weight being further preferred, and 25 to 75 parts by weight being particularly preferred.

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

[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, their total amount 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 can be crosslinked 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 backbone. 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 3000 parts by mass or less, which is preferred; 2000 parts by mass or less, which is even better; 1000 parts by mass or less, which is further preferred; 500 parts by mass or less, which is even more preferred; and 200 parts by mass or less, which is especially preferred.

[0107] <<Polymerizing Resins>> The photosensitive composition of the present invention comprises a polymeric resin D (hereinafter referred to as polymeric resin) having a group containing an ethylene unsaturated bond. Examples of ethylene unsaturated bonds in the polymeric resin include vinyl, (methyl)allyl, and (meth)acrylyl groups.

[0108] The weight average molecular weight of the polymerizable resin is preferably above 3000, 3000~50000 is even better, 5000~50000 is further better, and 5000~40000 is particularly good.

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

[0110] The polymerizable resin is preferably a resin containing repeating units with side chains having 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 vinyl unsaturated bonds is preferably 10 mol% or more among all repeating units of the polymerizable resin, more preferably 10-80 mol%, and further preferably 20-70 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] Examples of trivalent linkages represented by X1 in formula (A-1-1) include poly(meth)acrylic acid linkages, polyalkylimide linkages, polyester linkages, polyurethane linkages, polyurea linkages, polyamide linkages, polyether linkages, and polystyrene linkages. Poly(meth)acrylic acid linkages, polyalkylimide linkages, and polyester linkages are preferred, with poly(meth)acrylic acid linkages being even more preferred.

[0113] Examples of divalent linkages represented by L1 in formula (A-1-1) 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. The alkyl groups in the alkyl groups, alkoxy groups, and oxoalkylcarbonyl groups can be linear, branched, or cyclic, with linear or branched forms being preferred. Furthermore, the alkyl groups in the alkyl groups, alkoxy groups, and oxoalkylcarbonyl groups can have substituents or can be unsubstituted. Examples of substituents include hydroxyl and alkoxy groups; from the viewpoint of manufacturing suitability, hydroxyl groups are preferred.

[0114] Examples of groups containing vinyl unsaturated bonds represented by Y1 in formula (A-1-1) include vinyl, (meth)allyl, (meth)acrylyl, and styryl, with (meth)acrylyl and styryl being preferred, (meth)acrylyl being even more preferred, and acrylylyl being particularly preferred.

[0115] As specific examples of repeating units represented by equation (A-1-1), we can cite repeating units represented by equation (A-1-1a) and repeating units represented by equation (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 linkage, 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] Polymerizable resins with grafted chains are preferred. Examples of resins with grafted chains include resins containing repeating units with grafted chains. Polymerizable resins with grafted chains are better suited for use as dispersants. When using polymerizable resins with grafted chains, during exposure, the polymerizable resin polymerizes near the colorant, thus firmly retaining the colorant in the film and effectively suppressing 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 500-30000, more preferably 1000-20000, and even more preferably 2000-10000.

[0120] The grafted chain preferably 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 repeating units represented by formulas (G-1), (G-4), or (G-5). Examples of repeating units of polyether structure include repeating units represented by formula (G-2). Examples of repeating units of poly(meth)acrylic acid structure include repeating units represented by formula (G-3). [Chemical Formula 16]

[0121] In the above formula, RG1 and RG2 represent alkyl groups, respectively. As alkyl groups represented by RG1 and RG2, linear or branched alkyl groups having 1 to 20 carbon atoms are preferred, linear or branched alkyl groups having 2 to 16 carbon atoms are more preferred, and linear 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 linkage. Examples of divalent linkages 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 (meth)acrylyl. Examples of cyclic ether groups include epoxy and oxocyclobutyl.

[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. 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] The polymeric resin is preferably a resin containing repeating units represented by the following formula (A-1-2). [Chemical Formula 17]

[0124] In equation (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] As specific examples of repeating units represented by equation (A-1-2), we can cite repeating units represented by equation (A-1-2a) and repeating units represented by equation (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 extended phenyl groups, L2 represents a single bond or a divalent linkage, and W1 represents a grafted chain. The alkyl groups represented by Rb1 to Rb3 preferably have 1 to 10 carbon atoms, 1 to 3 are more preferred, and 1 is further preferred. Qb1 is preferably -COO- or -CONH-, with -COO- being more preferred.

[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. The carbon number of the alkyl groups represented by Rb10 and Rb11 is preferably 1 to 10, and 1 to 3 is even more preferred.

[0129] When a 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 a 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 in the polymeric resin, and more preferably 1.5 to 50 mol%.

[0131] It is 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 a polymeric resin contains repeating units with acid groups, it is preferable that the content of repeating units with acid groups is 80 mol% or less, and more preferably 10-80 mol% among all repeating units in the polymeric resin. When a polymeric resin contains repeating units with acid groups, it is preferable that the acid value of the polymeric resin is 20-150 mg KOH / g. The upper limit is preferably 100 mg KOH / g or less, and the lower limit is preferably 30 mg KOH / g or more, and more preferably 35 mg KOH / g or more. When the acid value of the polymeric resin is within the above range, excellent dispersibility is particularly easy to obtain. Furthermore, excellent developability is easily obtained.

[0133] Polymerizable resins containing repeating units represented by formula (Ac-1) are also preferred. [Chemical Formula 19] In formula (Ac-1), Ar10 represents a group containing an aromatic carboxyl group, L11 represents -COO- or -CONH-, L12 represents a trivalent linker, and P10 represents a polymer chain containing a group with an ethylene unsaturated bond.

[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. Examples of aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds with the following structures. [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, where 1 or 2 is preferred, and 2 is even better. In formula (Ar-12), n2 represents an integer from 1 to 8, where an integer from 1 to 4 is preferred, 1 or 2 is even better, and 2 is even better. In equation (Ar-13), n3 and n4 independently represent integers from 0 to 4, with integers from 0 to 2 being preferred, 1 or 2 being more preferred, and 1 being even more preferred. 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 equations (Ar-11) to (Ar-13), *1 represents the bond position with L11.

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

[0138] Examples of trivalent linkages represented by L12 in formula (Ac-1) include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups formed by combining 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. Hydrocarbon groups may have substituents. Examples of substituents include hydroxyl groups. Examples of trivalent linkages represented by L12 are preferably groups represented by formula (L12-1), and even more preferably groups 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 trivalent linkers represented by L12b include hydrocarbon groups; groups formed by combining a hydrocarbon group with at least one of -O-, -CO-, -COO-, -OCO-, -NH-, and -S- are preferred, especially those consisting of a hydrocarbon group or a combination of a hydrocarbon group and -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). As the trivalent linker represented by L12c, a hydrocarbon group can be cited; a hydrocarbon group combined with at least one group selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S- is preferred.

[0141] In formula (Ac-1), P10 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, with 90% by mass or less being preferable, and 60% by mass or less being even more preferable.

[0143] Furthermore, it is preferable that the polymer chain represented by P10 contains repeating units including 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 further preferably 3 to 10% by mass.

[0144] The weight-average molecular weight of the polymer chain represented by P10 is preferably between 500 and 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 dispersibility in the composition is good. 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 below 25,000, more preferably below 20,000, and further preferably below 15,000. The lower limit is preferably above 4,000, more preferably above 5,000, and further preferably above 6,000.

[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 below 150 mg KOH / g, more preferably below 100 mg KOH / g, and further preferably below 80 mg KOH / g. The lower limit is preferably above 10 mg KOH / g, more preferably above 15 mg KOH / g, and further preferably above 20 mg KOH / g.

[0147] The content of polymeric resin in the total solids of the photosensitive composition is preferably 1-40% 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 percentage of polymerizable monomers and polymerizable resins in the total solids composition of the photosensitive component is preferably 5-45% 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, their total amount is within the above-mentioned range.

[0149] <<Other Resins>> The photosensitive composition of the present invention can contain resins other than the polymeric 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. Additionally, resins primarily used for dispersing pigments are also referred to as dispersants. However, this use of resins is only one example; they can also be used for purposes other than these.

[0150] For other resins, a weight-average molecular weight (Mw) of 3,000 to 2,000,000 is preferred. An upper limit of less than 1,000,000 is more preferred, and less than 500,000 is even more preferred. A lower limit of more than 4,000 is more preferred, and more than 5,000 is even more preferred.

[0151] Other resins include (meth)acrylic resins, olefin-thiol resins, polycarbonate resins, polyether resins, polyaryl ester resins, polyurethane resins, polyetherurethane resins, polystyrene resins, polyaryl ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins. 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 containing acid groups are preferred. This improves the developability of the pixel-forming composition. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups, with carboxyl groups being preferred. For example, resins containing acid groups can be used as alkali-soluble resins. It is preferable that the resin containing acid groups comprises repeating units with acid groups in the side chains, and it is even more preferable that the resin contains 5 to 70 mol% of repeating units with acid groups in the side chains in all repeating units. It is further preferred that the upper limit of the content of repeating units with acid groups in the side chains is 50 mol% or less, and particularly preferred that it is 30 mol% or less. It is further preferred that the lower limit of the content of repeating units with acid groups in the side chains is 10 mol% or more, and particularly preferred that it is 20 mol% or more. Regarding resins containing acid groups, reference can be made to paragraphs 0558-0571 of Japanese Patent Application Publication No. 2012-208494 (corresponding to paragraphs 0685-0700 of U.S. Patent Application Publication No. 2012 / 0235099) and paragraphs 0076-0099 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 that is essentially 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 mgKOH / g, more preferably 50~105 mgKOH / g, and further preferably 60~105 mgKOH / g. Similarly, 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 sum of the amount of acid groups and the amount of base groups is set to 100 mol%, resins with a base group content 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, and this content is incorporated herein by reference. 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 contains 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 can 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; this content is incorporated into this specification. 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 composition of the photosensitive component 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. Other resins may be only one type or two or more types. When two or more types are included, it is preferable that their total amount be 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 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, isoindoleline ketone 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 below 3000 L·mol⁻¹·cm⁻¹, more preferably below 1000 L·mol⁻¹·cm⁻¹, and further preferably below 100 L·mol⁻¹·cm⁻¹. For example, the lower limit of εmax is above 1 L·mol⁻¹·cm⁻¹, and can also be above 10 L·mol⁻¹·cm⁻¹.

[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 Publication No. 2. Paragraphs 0086-0098 of Japanese Patent Application Publication No. 011 / 024896, paragraphs 0063-0094 of International Patent Application Publication No. 2012 / 102399, paragraph 0082 of International Patent Application Publication No. 2017 / 038252, paragraph 0171 of Japanese Patent Application Publication No. 2015-151530, paragraphs 0162-0183 of Japanese Patent Application Publication No. 2011-252065, and Japanese Patent Application Publication No. 2015-151530. The compounds described in Japanese Patent Publication No. 2003-081972, Japanese Patent Publication No. 5299151, Japanese Unexamined Patent Publication No. 2015-172732, Japanese Unexamined Patent Publication No. 2014-199308, Japanese Unexamined Patent Publication No. 2014-085562, Japanese Unexamined Patent Publication No. 2014-035351, and Japanese Unexamined Patent 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 can be used simultaneously. When two or more are used simultaneously, the total amount within the above-mentioned range is preferred.

[0159] <<Polyalkylimide>> The photosensitive composition of the present invention may also contain polyalkylimide. Polyalkylimide is a polymer formed by ring-opening polymerization of alkylimide, and is a polymer having a branched structure comprising primary, secondary, and tertiary amino groups respectively. A carbon number of 2 to 6 is preferred for the alkylimide, 2 to 4 is more preferred, 2 or 3 is further preferred, and 2 is particularly preferred.

[0160] The molecular weight of 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 polyalkylimide, when the molecular weight can be calculated from the structural formula, the molecular weight of 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 polystyrene 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 polyalkylene imides include ethyleneimine, propyleneimine, 1,2-buteneimine, and 2,3-buteneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being even more preferred. Polyalkylene imides, particularly polyethyleneimine, are especially preferred. Furthermore, in polyethyleneimine, it is preferable to contain 10 mol% or more of primary amino groups relative to the total number of primary, secondary, and tertiary amino groups, more preferably 20 mol% or more, and even more preferably 30 mol% or more. Commercially available polyethyleneimine products 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 within the above-mentioned range is preferred.

[0164] <<Compounds with cyclic ether groups>> The photosensitive composition of the present invention can contain a compound having a cyclic ether group. Examples of cyclic ether groups include epoxy groups and oxocyclobutyl groups. It is preferred that the compound having a cyclic ether group is a compound having an epoxy group (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 preferred 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 preferred that the lower limit of the number of epoxy groups contained in the epoxy compound is two or more. As epoxy 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] Epoxy compounds can be low molecular weight compounds (e.g., molecular weight less than 2000, and further less than 1000) or macromolecules (e.g., molecular weight greater than 1000; in the case of polymers, the weight average molecular weight is greater than 1000). It is preferable for compounds containing epoxy groups to have a weight average molecular weight of 200 to 100,000, and more preferably 500 to 50,000. It is further preferable for the upper limit of the weight average molecular weight to be less than 10,000, particularly preferred to be less than 5,000, and even more preferably less than 3,000.

[0166] Epoxy resins are preferred as epoxy compounds. Examples of epoxy resins include, for instance, epoxy resins that are epoxy propylene oxide ethers of phenolic compounds, epoxy resins that are epoxy propylene oxide ethers of various phenolic varnish resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, epoxy propylene ester-based epoxy resins, epoxy propylene amine-based epoxy resins, epoxy resins obtained by epoxypropylating halogenated phenols, fused compounds of epoxy-based silicone compounds and other silicone compounds, and copolymers of epoxy-based polymerizable unsaturated compounds 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 further 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 manufactured by NOF CORPORATION and containing epoxy groups).

[0168] The content of compounds having cyclic ether groups in the total solids of the photosensitive composition is preferably 0.1 to 20% by mass. For example, a lower limit of 0.5% by mass or more is more preferred, and 1% by mass or more is further preferred. For example, an upper limit of 15% by mass or less is more preferred, and 10% by mass or less is further preferred. Only one compound having cyclic ether groups may be used, or two or more compounds may be used. When two or more compounds are used, it is preferable that their total content is within the above-mentioned range.

[0169] <<Hardening Accelerator>> The photosensitive composition of the present invention may include a curing accelerator. Examples of curing accelerators include thiols, hydroxymethyl compounds, amine compounds, phosphonium salts, amidine salts, amide compounds, alkali-generating agents, isocyanate compounds, alkoxysilane compounds, and onium salts. Specific examples of curing accelerators include compounds described in paragraphs 0094-0097 of International Publication No. 2018 / 056189, compounds described in paragraphs 0246-0253 of Japanese Patent Application Publication No. 2015-034963, compounds described in paragraphs 0186-0251 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 epoxy curing agents containing carboxyl groups 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] <<Surfactants>> 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. Furthermore, it is also possible to form a film with less thickness unevenness.

[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 within this range are effective in terms of coating film thickness uniformity and liquid-saving properties, and also have good solubility in photosensitive components.

[0173] Examples of fluorinated surfactants include those described in Japanese Patent Application Publication No. 2014-041318 (paragraphs 0060-0064 of the corresponding International Publication No. 2014 / 017669), Japanese Patent Application Publication No. 2011-132503 (paragraphs 0117-0132), and Japanese Patent Application Publication No. 2020-008634, the contents of which are included in this specification. Commercially available 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 molecular structures with functional groups containing fluorine atoms, and whose functional groups containing fluorine atoms are cleaved upon heating, causing the fluorine atoms to volatilize. 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 use 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 0016-0037 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 3,000 to 50,000, for example, 14,000. In the above compounds, the percentage of repeating units is expressed in moles.

[0177] Furthermore, fluorinated surfactants can also be used on fluoropolymers with ethylene-unsaturated groups 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, compounds described in paragraphs 0015-0158 of Japanese Patent Application Publication No. 2015-117327 can also be used as fluorinated surfactants.

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

[0179] Furthermore, it is also preferable to use fluoroimidide salt compounds represented by formula (fi-1) as surfactants. [Chemical Formula 25] In formula (fi-1), m represents 1 or 2, n represents an integer from 1 to 4, α represents 1 or 2, and Xα+ represents an α-valent metal ion, a primary ammonium ion, a secondary ammonium ion, a tertiary ammonium ion, a quaternary ammonium ion, or NH4+.

[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 structures can also be used in polysiloxane 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. The type of solvent is not particularly limited 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, organic solvents with a metal content of less than 10 ppb (parts per billion). Organic solvents at the ppt (parts per trillion) level can be used as needed, such organic solvents are provided 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. For the filter used in filtration, a pore size of 10 μm or less is preferred, 5 μm or less is more preferred, and 3 μm or less is even more preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0187] Organic solvents can contain isomers (compounds with the same number of atoms but different structures). Furthermore, isomers can be a single type or a plurality of types.

[0188] The content of peroxide in organic solvents is preferably below 0.8 mmol / L, and it is even better if there is no peroxide at all.

[0189] The solvent content in the photosensitive component is preferably 10-95% by mass. The upper limit is preferably 92.5% by mass or less, and even more preferably 90% by mass or less. From the viewpoint of coatability, the lower limit is preferably 20% by mass or more, even 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 addition, 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 substances 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 other 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 Agents>> The photosensitive composition of the present invention can 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 directly bonds 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 acetoxy groups, with alkoxy groups being preferred. That is, a silane coupling agent having an alkoxysilyl group is preferred. Furthermore, examples of functional groups other than the hydrolyzable group include vinyl, (meth)allyl, (meth)acrylyl, mercapto, epoxy, oxetyl, amino, urea, thioether, isocyanate, and phenyl groups, with amino, (meth)acrylyl, and epoxy groups being 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 Absorbers>> 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 triterene compound, an indole compound, a triterene compound, etc. Examples of such compounds include those described in Japanese Patent Application Publication No. 2009-217221 (paragraphs 0038-0052), Japanese Patent Application Publication No. 2012-208374 (paragraphs 0052-0072), Japanese Patent Application Publication No. 2013-068814 (paragraphs 0317-0334), and Japanese Patent Application Publication No. 2016-162946 (paragraphs 0061-0080), the contents of which are incorporated herein by reference. Commercially available ultraviolet absorbers include, for example, UV-503 (manufactured by DAITO CHEMICAL CO.,LTD.). Furthermore, examples of benzotriazole compounds include the MYUA series manufactured by MIYOSHI OIL & FAT CO.,LTD. (Chemical Industry Daily, February 1, 2016). Additionally, the ultraviolet absorber can also be the compounds described in paragraphs 0049-0059 of Japanese Patent No. 6268967. The content of the ultraviolet absorber in the total solids of the photosensitive component is preferably 0.01-10% by mass, and more preferably 0.01-5% 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] Antioxidants 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 position (ortho) adjacent to the phenolic hydroxyl group 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 within 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 Inhibitors>> 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 polymerization inhibitor, or there may be two or more. In the case of two or more, the total amount within the above range is preferred.

[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 components, the physical properties of the film can be adjusted. Regarding these components, 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 0034-0047 of the Japanese Patent Application Publication No. 2015-025116, the compounds described in paragraphs 0019-0041 of the Japanese Patent Application Publication No. 2012-145604, the compounds described in paragraphs 0101-0125 of the Japanese Patent Application Publication No. 2012-103475, the compounds described in paragraphs 0018-0021 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 practically non-existent is particularly preferred. 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" means that the content of terephthalate in the total amount of the photosensitive composition is less than 1000 ppb by mass, less than 100 ppb by mass 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 aforementioned 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 further 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. As compounds that can serve as substitutes for controlled compounds, examples include compounds 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] <<Containment Container>> There are no particular restrictions on the container used to contain the photosensitive component, and known containers can be used. However, for the purpose of preventing impurities from contaminating the raw materials and photosensitive component, multi-layered bottles with an inner wall composed of six layers of six different resins, or bottles with a seven-layer structure of the six resins, are preferable. 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 component, or inhibiting component deterioration, it is preferable to use glass or stainless steel.

[0201] <Preparation method of photosensitive components> 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 then mixed together before use (during 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. Moreover, 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 dispersants, the processes and dispersants 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. Also, 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 to remove impurities and reduce defects. As for the filter, any filter that has been used for filtration purposes can be used without particular limitation. Examples of filters made from raw materials include fluoropolymers such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight polyolefin resins). Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0204] The pore size of the filter is preferably 0.01~7.0μm, more preferably 0.01~3.0μm, and further preferably 0.05~0.5μm. As long as the filter pore size is within the above range, fine foreign matter can be removed more effectively. For filter pore size values, please refer to the filter manufacturer's specifications. 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., filter 1 and filter 2). 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] <Filter Manufacturing Method> Next, the manufacturing method of the filter of the present invention will be described. Examples of filters include color filters, near-infrared cut-off filters, and near-infrared transmittance filters. The manufacturing method of the filter of 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 the 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] The coating method for the photosensitive component can be any known method. 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 and other ejection systems; flexographic printing; screen printing; gravure printing; reverse offset printing; metal mask printing and other methods; transfer printing using molds; nanoimprinting, etc. 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 is not 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 above 50°C, or above 80°C. The pre-baking time is preferably 10–300 seconds, more preferably 40–250 seconds, and further preferably 80–220 seconds. Pre-baking can be performed using a heating plate, oven, or similar equipment.

[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 portions of the photosensitive composition layer to be cured.

[0212] The light used for exposure can be any light with a wavelength of less than 300 nm, 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, light can be continuously irradiated for exposure, or pulsed irradiation can be performed for exposure (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 achieve exposure.

[0214] The optimal exposure concentration (irradiance) is 0.03–2.5 J / cm², with 0.05–1.0 J / cm² being even better. The oxygen concentration during exposure can be appropriately selected. Exposure can be performed not only in atmospheric conditions but also in low-oxygen environments (e.g., 15% or 5% by volume, or virtually oxygen-free) or high-oxygen environments (e.g., 22%, 30%, or 50% by volume) with oxygen concentrations exceeding 21% by volume. Furthermore, the 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 illuminance can be appropriately combined, for example, with an oxygen concentration of 10% by volume and an illuminance of 10000 W / m², or an oxygen concentration of 35% by volume and an illuminance of 20000 W / m².

[0215] Next, development removes the unexposed portions of the photosensitive composition layer from the photosensitive composition layer after the exposure step. In this process, the unexposed portions of the photosensitive composition layer from the exposure step dissolve into the developing solution, leaving only the photocured portion to form a pixel.

[0216] For example, the optimal temperature for the developer is 20-30°C. The optimal development time is 20-180 seconds. Furthermore, to improve residue removal, the following steps can be repeated several times: discarding the developer every 60 seconds and then supplying fresh developer.

[0217] Developers can include organic solvents and alkaline developers, with alkaline developers being preferred. An alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferred. Examples of alkaline agents include, for example, 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, 1,8-diazabicyclo[5.4.0]-7-undecene, and other organic alkaline compounds, 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 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. When moving the nozzle from the center to the periphery, the nozzle can be moved while gradually reducing its moving speed. 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 and heating treatment (post-baking) after drying. Additional exposure and post-baking are curing treatments performed 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, light with a wavelength of 400nm or less is preferable. Furthermore, the additional exposure can be performed using the method described in Korean Patent Publication No. 10-2017-0122130.

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

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

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

[0222] <Manufacturing Methods of Solid-State Imaging Components> 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 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 a transmission electrode formed of polysilicon, etc. A light-shielding film with openings only in the light-receiving portion of the photodiodes is present on the photodiodes and the transmission electrode. An element protective film formed of silicon nitride, etc., is present on the light-shielding film, covering 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 present on the element protective film. Furthermore, the structure may have a light-gathering mechanism (e.g., a microlens, etc. The same applies hereinafter) on the element protective film and on the underside (closer to the substrate) of the filter, or a structure with a light-gathering mechanism 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 method for manufacturing an image display device. This manufacturing method includes the method for manufacturing the filter 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 this invention can be applied; for example, liquid crystal display devices of various types described in "Next-Generation Liquid Crystal Display Technology" can be applied. [Example]

[0225] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, and processing order shown in the following examples 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> Types of tubing: Tubing that connects 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) Device Name: Tosoh Corporation HLC-8220GPC Detector: RI (Refractive Index) Detector Calibration curve matrix resin: polystyrene resin

[0227] <Preparation of Dispersions> 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] pigment Dispersing agents, pigment derivatives Dispersant 1 Dispersant 2 solvent type Dosage (parts by weight) type Dosage (parts by weight) type Dosage (parts by weight) type Dosage (parts by weight) type Dosage (parts by weight) Dispersant G1 PG58 11.86 D-1 0.41 B-1 3.73 - - S-1 84 Dispersant G2 PG58 11.86 D-1 0.41 B-2 3.73 - - S-1 84 Dispersant G3 PG58 11.86 D-1 0.41 B-3 3.73 - - S-1 84 Dispersant G4 PG58 11.86 D-1 0.41 B-4 3.73 - - S-1 84 Dispersant G5 PG58 11.86 D-1 0.41 B-5 3.73 - - S-1 84 Dispersant G6 PG58 11.86 D-1 0.41 B-1 2.61 E-1 1.12 S-1 84 Dispersant G7 PG36 11.86 D-1 0.41 B-1 3.73 - - S-1 84 Dispersant G8 PG58 11.86 D-2 0.41 B-1 3.73 - - S-1 84 Dispersant G9 PG58 11.86 D-3 0.41 B-1 3.73 - - S-1 84 Dispersant G10 PG58 11.86 A-1 0.41 B-1 3.73 - - S-1 84 Dispersant G11 PG58 11.86 A-1 0.41 B-1 3.73 - - S-1 S-2 67.2 16.8 Dispersant G12 PG58 11.86 A-1 0.41 B-1 3.73 - - S-1 S-3 79.8 4.2 Dispersant G13 PG58 11.86 A-1 0.41 B-1 3.73 - - S-1 S-4 75.6 8.4 Dispersant G14 PG58 11.86 A-1 0.41 B-1 3.73 - - S-1 S-5 67.2 16.8 Dispersant G15 PG58 11.86 A-1 0.41 B-1 2.61 E-1 1.12 S-1 S-3 79.8 4.2 Dispersant Gc1 PG58 11.86 D-1 0.41 - - E-1 3.73 S-1 84 Dispersant Y1 PY185 10.08 D-1 1.78 B-1 4.14 - - S-1 84 Dispersant Y2 PY185 10.08 D-1 1.78 B-2 4.14 - - S-1 84 Dispersant Y3 PY185 10.08 D-1 1.78 B-3 4.14 - - S-1 84 Dispersant Y4 PY185 10.08 D-1 1.78 B-4 4.14 - - S-1 84 Dispersant Y5 PY185 10.08 D-1 1.78 B-5 4.14 - - S-1 84 Dispersant Y6 PY215 10.08 D-1 1.78 B-1 4.14 - - S-1 84 Dispersant Y7 PY129 10.08 D-1 1.78 B-1 4.14 - - S-1 84 Dispersant Y8 PY185 10.08 D-2 1.78 B-1 4.14 - - S-1 84 Dispersant Y9 PY139 10.67 D-1 1.19 B-1 4.14 - 0 S-1 84 Dispersant Y10 PY139 10.67 D-2 1.19 B-1 4.14 - 0 S-1 84 Dispersant Y11 PY139 10.67 D-1 1.19 - - E-1 E-2 2.07 2.07 S-1 84 Dispersant Yc1 PY185 10.08 D-1 1.78 - - E-1 4.14 S-1 84 Dispersant R1 PR254 10.67 D-1 1.19 B-1 4.14 - - S-1 84 Dispersant R2 PR272 10.67 D-1 1.19 B-1 4.14 - - S-1 84 Dispersant R3 PR254 PR272 5.335 5.335 D-1 1.19 B-1 4.14 - - S-1 84 Dispersant R4 PR254 10.67 D-4 1.19 B-1 4.14 - 0 S-1 84 Dispersant R5 PR254 PR272 5.335 5.335 D-4 1.19 B-1 4.14 - 0 S-1 84 Dispersant R6 PR254 10.67 D-1 1.19 - - E-2 4.14 S-1 84

[0229] The detailed information for the abbreviations of the raw materials listed in the table above is 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 value (C=C value) containing vinyl unsaturated bonds are shown in the table below). [Chemical Formula 28] [Table 2] x y z Mw C=C value (mmol / g) B-1 62 25 13 20000 0.24 B-2 62 16 twenty two 20000 0.46 B-3 52 18 31 20000 0.68 B-4 64 twenty four 12 20000 0.19 B-5 70 27 3 20000 0.04

[0233] [Dispersant 2] E-1: Resins with the following structure (resins that do not contain groups containing vinyl unsaturated bonds. The values ​​indicated in the main chain are molars, 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] E-2: Resins with the following structure (resins that do not contain groups containing vinyl unsaturated bonds. The values ​​indicated in the main chain are molars, and the values ​​indicated in the side chains are the number of repeating units. The weight average molecular weight is 21,000). [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 Components> The photosensitive composition was manufactured by mixing the raw materials listed in the table below. [Table 3] Dispersion Polymerizable monomers resin Dispersion 1 Dispersion 2 type Dosage (parts by weight) type Dosage (parts by weight) type Dosage (parts by weight) type Dosage (parts by weight) Example 1 Dispersion G1 55.15 Dispersion Y1 19.85 M-1 1.91 C-1 0.54 Example 2 Dispersion G1 55.15 Dispersion Y1 19.85 M-2 1.91 C-1 0.54 Example 3 Dispersion G1 55.15 Dispersion Y1 19.85 M-3 1.91 C-1 0.54 Example 4 Dispersion G1 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 5 Dispersion G2 55.15 Dispersion Y2 19.85 M-2 1.91 C-1 0.54 Example 6 Dispersion G3 55.15 Dispersion Y3 19.85 M-2 1.91 C-1 0.54 Example 7 Dispersion G4 55.15 Dispersion Y4 19.85 M-2 1.91 C-1 0.54 Example 8 Dispersion G5 55.15 Dispersion Y5 19.85 M-2 1.91 C-1 0.54 Example 9 Dispersion G2 55.15 Dispersion Y2 19.85 M-4 1.91 C-1 0.54 Example 10 Dispersion G3 55.15 Dispersion Y3 19.85 M-4 1.91 C-1 0.54 Example 11 Dispersion G4 55.15 Dispersion Y4 19.85 M-4 1.91 C-1 0.54 Example 12 Dispersion G5 55.15 Dispersion Y5 19.85 M-4 1.91 C-1 0.54 Example 13 Dispersion G1 55.15 Dispersion Y1 19.85 M-4 2.16 C-1 0.29 Example 14 Dispersion G1 55.15 Dispersion Y1 19.85 M-4 2.45 - - Example 15 Dispersion G1 55.15 Dispersion Y1 19.85 M-4 / M-2 0.955 / 0.955 C-1 0.54 Example 16 Dispersion G1 58.95 Dispersion Y1 21.05 M-4 1.91 - - Example 17 Dispersion G1 64.05 Dispersion Y1 twenty three M-4 0.65 - - Example 18 Dispersion G1 51.25 Dispersion Y1 18.15 M-4 1.91 C-1 1.85 Example 19 Dispersion G6 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 20 Dispersion G1 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.12 Example 21 Dispersion G1 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.79 Example 22 Dispersion G1 55.15 Dispersion Y6 19.85 M-4 1.91 C-1 0.54 Example 23 Dispersion G1 55.15 Dispersion Y7 19.85 M-4 1.91 C-1 0.54 Example 24 Dispersion G7 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 25 Dispersion G8 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 26 Dispersion G9 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 27 Dispersion G10 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 28 Dispersion G11 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 29 Dispersion G12 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 30 Dispersion G13 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 31 Dispersion G14 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 32 Dispersion G15 55.15 Dispersion Y1 19.85 M-4 1.91 C-1 0.54 Example 33 Dispersion G1 55.15 Dispersion Y8 19.85 M-4 1.91 C-1 0.54 Example 34 Dispersion G8 55.15 Dispersion Y8 19.85 M-4 1.91 C-1 0.54 Example 35 Dispersion G9 55.15 Dispersion Y8 19.85 M-4 1.91 C-1 0.54 Example 36 Dispersion R1 55.15 Dispersion Y9 19.85 M-4 1.91 C-1 0.54 Example 37 Dispersion R2 55.15 Dispersion Y9 19.85 M-4 1.91 C-1 0.54 Example 38 Dispersion R3 55.15 Dispersion Y9 19.85 M-4 1.91 C-1 0.54 Example 39 Dispersion R4 55.15 Dispersion Y9 19.85 M-4 1.91 C-1 0.54 Example 40 Dispersion R5 55.15 Dispersion Y9 19.85 M-4 1.91 C-1 0.54 Example 41 Dispersion R4 55.15 Dispersion Y10 19.85 M-4 1.91 C-1 0.54 Example 42 Dispersion R5 55.15 Dispersion Y10 19.85 M-4 1.91 C-1 0.54 Example 43 Dispersion R6 49.27 Dispersion Y11 23.45 M-5 1.25 C-1 1.02 Comparative Example 1 Dispersion G1 55.15 Dispersion Y9 19.85 - - C-1 2.45 Comparative Example 2 Dispersion Gc1 55.15 Dispersion Yc1 19.85 M-4 1.91 C-2 0.54 [Table 4] Photopolymerization initiator surfactants Polymer inhibitors solvent type Dosage (parts by weight) type Dosage (parts by weight) type Dosage (parts by weight) type Dosage (parts by weight) Example 1 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 2 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 3 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 4 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 5 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 6 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 7 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 8 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 9 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 10 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 11 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 12 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 13 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 14 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 15 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 16 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 17.59 Example 17 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 11.8 Example 18 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 26.34 Example 19 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 20 I-1 0.9 W-1 0.01 Q-1 0.01 S-1 22.05 Example 21 I-1 0.23 W-1 0.01 Q-1 0.01 S-1 22.05 Example 22 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 23 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 24 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 25 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 26 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 27 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 28 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 29 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 30 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 31 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 32 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 33 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 34 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 35 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 36 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 37 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 38 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 39 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 40 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 41 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 42 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Example 43 I-1 0.38 W-1 0.01 Q-1 0.01 S-1 24.61 Comparative Example 1 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05 Comparative Example 2 I-1 0.48 W-1 0.01 Q-1 0.01 S-1 22.05

[0236] The content of colorant in the total solids of each photosensitive component, the content of polymerizable monomer in the total solids of the photosensitive component, the mass fraction of polymerizable monomer relative to 100 parts by mass of polymerizable resin, the basic value of vinyl unsaturated bonds from polymerizable monomer in the total solids of the photosensitive component (C=C value 1), and the basic value of vinyl unsaturated bonds from polymerizable resin 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 and the C=C value of each polymeric monomer in the total solids component of the photosensitive composition by the total amount of solids component of the photosensitive composition. Similarly, C=C value 2 is calculated by dividing 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 component of the photosensitive composition by the total amount of solids component of the photosensitive composition. 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] Colorant content (mass %) Content of polymerizable monomers (quality%) The mass parts of polymeric monomer relative to 100 parts by mass of polymeric resin C = C value 1 (mmol / g) C = C value 2 (mmol / g) Example 1 57.55 12.78 55.87 1.27 0.10 Example 2 57.55 12.78 55.87 1.29 0.10 Example 3 57.55 12.78 55.87 1.45 0.10 Example 4 57.55 12.78 55.87 0.27 0.10 Example 5 57.55 12.78 55.87 1.29 0.14 Example 6 57.55 12.78 55.87 1.29 0.18 Example 7 57.55 12.78 55.87 1.29 0.09 Example 8 57.55 12.78 55.87 1.29 0.06 Example 9 57.55 12.78 55.87 0.27 0.14 Example 10 57.55 12.78 55.87 0.27 0.18 Example 11 57.55 12.78 55.87 0.27 0.09 Example 12 57.55 12.78 55.87 0.27 0.06 Example 13 57.55 14.45 68.16 0.31 0.07 Example 14 57.55 16.39 85.10 0.35 0.05 Example 15 57.55 12.78 55.87 0.78 0.10 Example 16 60.35 12.56 62.21 0.27 0.05 Example 17 66.23 4.31 19.45 0.09 0.05 Example 18 51.84 12.43 42.32 0.26 0.21 Example 19 57.55 12.78 68.18 0.27 0.09 Example 20 57.55 12.78 63.69 0.27 0.06 Example 21 57.55 12.78 52.06 0.27 0.12 Example 22 57.55 12.78 55.87 0.27 0.10 Example 23 57.55 12.78 55.87 0.27 0.10 Example 24 57.55 12.78 55.87 0.27 0.10 Example 25 57.55 12.78 55.87 0.27 0.10 Example 26 57.55 12.78 55.87 0.27 0.13 Example 27 57.55 12.78 55.87 0.27 0.10 Example 28 57.55 12.78 55.87 0.27 0.10 Example 29 57.55 12.78 55.87 0.27 0.10 Example 30 57.55 12.78 55.87 0.27 0.10 Example 31 57.55 12.78 55.87 0.27 0.10 Example 32 57.55 12.78 68.18 0.27 0.09 Example 33 57.55 12.78 55.87 0.27 0.10 Example 34 57.55 12.78 55.87 0.27 0.10 Example 35 57.55 12.78 55.87 0.27 0.13 Example 36 55.18 12.78 52.40 0.27 0.10 Example 37 55.18 12.78 52.40 0.27 0.10 Example 38 55.18 12.78 52.40 0.27 0.10 Example 39 55.18 12.78 52.40 0.27 0.10 Example 40 55.18 12.78 52.40 0.27 0.10 Example 41 55.18 12.78 52.40 0.27 0.10 Example 42 55.18 12.78 52.40 0.27 0.10 Example 43 55.92 8.74 122.55 0.66 0.10 Comparative Example 1 57.55 0.00 0.00 0.00 0.28 Comparative Example 2 57.55 12.78 - 0.27 0.00

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

[0239] [Polymerizable monomers] M-1: Compounds with the following structure (C=C value: 9.94 mmol / g) [Chemical Formula 31] M-2: A mixture of compounds with the following structures (compound with the structure on the left:compound with the structure on the right = 7:3 (mass ratio), C=C value: 10.12 mmol / g) [Chemical Formula 32] M-3: Compounds with the following structure (C=C value: 11.35 mmol / g) [Chemical Formula 33] M-4: Compounds with the following structure (C=C value: 2.12 mmol / g) [Chemical Formula 34] M-5: Compounds with the following structure (C=C value: 7.57 mmol / g) [Chemical Formula 35]

[0240] [Resin] C-1: Resins with the following structure (polymeric resins. Values ​​indicated in the main chain are molars. Weight average molecular weight is 11000, C=C value: 1.44 mmol / g) [Chemical Formula 36] C-2: Resins with the following structure (the values ​​indicated in the main chain are in moles. Weight average molecular weight 14000). [Chemical Formula 37]

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

[0242] [Surfactants] W-1: Compounds with the following structure (fluorinated surfactants, 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 the optical micro-shadow properties> On an 8-inch (203.2 mm) silicon wafer with an undercoat, the photosensitive components obtained above were spin-coated using an Act8 wafer manufactured by OKYO Electron Limited to achieve a film thickness of 0.4 μm. The wafer was then heated at 100°C for 2 minutes using a hot plate to form the component layer. Next, the component 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 exposure, the exposed component 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. Finally, the wafer was rinsed with pure water using a rotating spray to form pixels. 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 a final determination. Evaluation results using a mask with a 0.7 μm square pattern are recorded in column 1 for photoresistivity, and evaluation results using a mask with a 0.6 μm square pattern are recorded in column 2 for photoresistivity. (Evaluation Criteria) 5: The straightness of the four sides of the pixel is good, and there is no residue between pixels. 4: The straightness of the four sides of the pixel is good, and there is little residue between pixels. 3: The four sides of the pixels are slightly rounded, and there is less residue between the pixels. 2: The pixels have rounded edges, and there is a lot of residue between the pixels. 1: Unable to form pixels.

[0246] [Table 6] Photolithography 1 Photomicrograph 2 Example 1 4 4 Example 2 4 4 Example 3 5 5 Example 4 5 5 Example 5 5 4 Example 6 5 5 Example 7 4 4 Example 8 4 3 Example 9 5 5 Example 10 5 5 Example 11 5 5 Example 12 5 4 Example 13 5 5 Example 14 5 4 Example 15 5 4 Example 16 5 4 Example 17 4 3 Example 18 5 5 Example 19 5 4 Example 20 5 5 Example 21 5 4 Example 22 5 5 Example 23 5 5 Example 24 5 5 Example 25 5 5 Example 26 5 5 Example 27 5 5 Example 28 5 5 Example 29 5 5 Example 30 5 5 Example 31 5 5 Example 32 5 4 Example 33 5 5 Example 34 5 5 Example 35 5 5 Example 36 5 5 Example 37 5 5 Example 38 5 5 Example 39 5 5 Example 40 5 5 Example 41 5 5 Example 42 5 5 Example 43 4 3 Comparative Example 1 3 2 Comparative Example 2 2 1

[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 the surfactants W-2 to W-44 as shown below.

[0249] W-2:FZ-2122 (manufactured by Dow Corning Toray Co., Ltd., a polysiloxane surfactant) W-3: BYK-322 (manufactured by BYK-Chemie GmbH, a polysiloxane surfactant) W-4: BYK-323 (manufactured by BYK-Chemie GmbH, a polysiloxane surfactant) W-5: BYK-330 (manufactured by BYK-Chemie GmbH, a polysiloxane surfactant) W-6: BYK-3760 (manufactured by BYK-Chemie GmbH, a polysiloxane surfactant) W-7: BYK-UV3510 (manufactured by BYK-Chemie GmbH, a 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) W-19: MEGAFACE F-565 (DIC Corporation, fluorinated surfactant) W-20: MEGAFACE F-568 (DIC Corporation, fluorinated surfactant) W-21: MEGAFACE F-575 (DIC Corporation, fluorinated surfactant) W-22: MEGAFACE R-01 (DIC Corporation, fluorinated surfactant) W-23: MEGAFACE R-40 (DIC Corporation, fluorinated surfactant) W-24: MEGAFACE R-40-LM (DIC Corporation, fluorinated surfactant) W-25: MEGAFACE R-41 (DIC Corporation, fluorinated surfactant) W-26: MEGAFACE R-41-LM (DIC Corporation, fluorinated surfactant) W-27: MEGAFACE R-94 (DIC Corporation, fluorinated surfactant) W-28: MEGAFACE DS-21 (DIC Corporation, fluorinated surfactant) W-29: MEGAFACE RS-43 (DIC Corporation, fluorinated surfactant) W-30: MEGAFACE RS-72-K (DIC Corporation, fluorinated surfactant) W-31: MEGAFACE RS-90 (DIC Corporation, fluorinated surfactant) W-32: MEGAFACE TF-1956 (DIC Corporation, fluorinated 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 surfactant) W-44:PF-6320 (manufactured by OMNOVA SOLUTIONS INC., a fluorinated surfactant)

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

[0251] -Blue photosensitive component- After mixing and stirring the following components, the mixture was filtered through a nylon filter (made by NIHON PALL LTD.) with a pore size of 0.45 μm, thereby preparing a blue photosensitive composition. Blue pigment dispersion 44.9 parts by weight Resin 101 2.1 parts by weight Polymer compound 101･･････1.5 parts by weight Polymerizable compound 102･･････0.7 parts by mass Photopolymerization initiator 101･･････0.8 parts by weight Surfactant 101･･････4.2 parts by weight PGMEA: 45.8 parts by weight

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

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

[0254] Resin 101: A 40% by mass solution of a resin with the following structure (the values ​​indicated in the main chain are molars; the weight average molecular weight is 11,000) containing PGMEA. [Chemical Formula 39] Polymer compound 101: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) Polymerizable compound 102: Compounds with the following structures [Chemical Formula 40] Photopolymerization initiator 101: Irgacure OXE02 (manufactured by BASF) Surfactant 101: A 1% PGMEA solution of a compound with the following structure (weight average molecular weight 14000, where in the following formula, % represents the proportion of repeating units in 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 comprises more than 50% by mass in the total solids content of the photosensitive composition, the polymerizable monomer C comprises more than 4% by mass in the total solids content of the photosensitive composition, and the polymerizable monomer C comprises 25 to 75 parts by mass relative to 100 parts by mass of the polymerizable resin D, wherein the polymerizable monomer C comprises a polymerizable monomer having a basal skeleton.

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 polymerizable monomer C comprises a 2-8 functional polymerizable 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 to 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 to 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 described in claim 1 or claim 2, wherein the photosensitive composition comprises two or more of the aforementioned polymeric resins D, and the aforementioned polymeric resins D comprise a resin containing repeating units represented by the following formula (A-1-1) and repeating units represented by the following formula (A-1-2); (in formula (A-1-1), X1 represents a trivalent linker, L1 represents a single bond or a divalent linker, and Y1 represents a group containing an ethylene unsaturated bond); (in formula (A-1-2), X2 represents a trivalent linker, L2 represents a single bond or a divalent linker, and W1 represents a grafted chain).

11. 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.

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

13. 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 12; 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.

14. The method of manufacturing a filter as claimed in claim 13, 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.

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